JP2011034732A - Conductive composition, conductor and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive composition, capable of obtaining a conductive thin film which is superior in adhesiveness to a base material and surface smoothness without requiring a complicated process, a conductor, and a method of manufacturing the same. <P>SOLUTION: This conductive composition contains (A) first organic acid metal salt, (B) at least one kind of amine selected from aliphatic polyamine, alicyclic polyamine and a nitrogen-containing heterocyclic compound having at least one amino group, (C) at least one kind of compound selected from among metal alkoxide and second organic acid metal salt (excluding organic acid metal salt, containing a metal contained in the first organic metal salt). This method of manufacturing the conductor includes a process of forming a coating film by applying the conductive composition on a base material, and a process to form a conductive film by baking the base material on which the coating film is formed at 150-900°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a conductive composition capable of forming a conductive thin film excellent in adhesion to a substrate, surface smoothness and metallic luster, a conductor using the same, and a method for producing the same.

A conductive film formed of a conductive material containing metal fine particles, an organic solvent, and the like is used for a wide range of electronic parts such as various electrodes, circuits, and capacitors. These conductive films are formed, for example, by forming a coating film made of a conductive material on a base material such as a glass substrate or a semiconductor substrate and baking it.

  In recent years, as typified by thin display panels such as portable information devices and LCDs, electronic components have become smaller and thinner, and miniaturization and higher density of circuits to which conductive films are applied have been required. . In order to form such an electronic component, the conductive film needs to have stronger adhesion and surface smoothness to the substrate.

  As a method for forming such a conductive film, a reducing agent is added to a first organic solvent containing silver ions and a protective agent such as alkylamine, and the filtrate obtained by filtering the precipitate is concentrated to form a solid. Then, a method for forming a silver thin film is proposed in which the solid is added to a second organic solvent, a paste obtained by further adding an organometallic compound is applied to a substrate, and fired at a temperature of 250 to 350 ° C. (Patent Document 1).

  In order to form a conductive film, a conductive ink containing an organic metal salt, a solvent, an adhesion improver such as a silane coupling agent, and a pH adjuster such as diethanolamine as necessary has been proposed. (Patent Document 2).

JP 2005-100980 A JP 2006-348160 A

However, in the method of forming a silver thin film of Patent Document 1, in order to obtain a silver thin film by low-temperature baking at 250 to 350 ° C., it is necessary to reduce solubilized silver ions to form fine particles, and the process is as follows. It is complicated.
In addition, in the conductive ink of Patent Document 2, when silver acetate or the like is used as the organic metal salt, the solubility of the conductive film obtained is not sufficient even when a pH adjuster such as diethanolamine is used. May be inferior to the adhesion and surface smoothness.

  The subject of this invention is providing the electroconductive composition which can form the electroconductive thin film which is excellent in adhesiveness and surface smoothness, and a manufacturing method therefor, without requiring a complicated process.

As a result of repeated studies to solve the above problems, the present inventors have used a specific amine and at least one compound selected from a metal alkoxide and a second organic acid metal salt to obtain a first It was found that a conductive composition capable of forming a conductive thin film with improved adhesion to the substrate and excellent surface smoothness can be obtained while increasing the solubility of the organic acid metal salt of .
[1] The present invention provides at least one selected from (A) a first organic acid metal salt, and (B) an aliphatic polyamine, an alicyclic polyamine, and a nitrogen-containing heterocyclic compound having at least one amino group. And at least one selected from (A) a metal alkoxide and a second organic acid metal salt (excluding an organic acid metal salt containing a metal contained in the first organic acid metal salt) It is an electroconductive composition containing a compound.
[2] The present invention is a conductor having a conductive film obtained by using the conductive composition.
[3] In the present invention, the step of forming a coating film made of the above conductive composition on a substrate and the substrate coated with the above conductive composition are baked at 150 to 900 ° C. to form a conductive film. A process for producing a conductor including a process.

In the present invention, the solubility of the first organic acid metal salt of the component (A) can be increased by the amine of the component (B), and the metal contained in the organic acid metal salt can be finely divided by a reducing agent or the like. It is possible to obtain a smooth and uniform conductive composition containing components (A), (B) and (C) without requiring a complicated process. Moreover, this invention is contained in the 1st organic acid metal salt of the component (A) at the time of baking by the at least 1 sort (s) of compound selected from the metal alkoxide of the component (C) and the 2nd organic acid metal salt. The conductive composition which forms the conductive thin film excellent in the adhesiveness to a base material, surface smoothness, and metal glossiness can be provided by suppressing aggregation of the metal which had been.
Moreover, according to the manufacturing method of this invention, even when it bakes at 150-900 degreeC, the conductor excellent in the adhesiveness and surface smoothness of the conductive thin film to a base material can be formed.

It is a SEM photograph image | photographed by 5000 time magnification about the electrically conductive thin film of Example 6. FIG. It is a SEM photograph imaged at a magnification of 5000 times for the conductive thin film of Comparative Example 2. It is a graph which shows the relationship between the baking temperature of the electrically conductive film of Example 1, 7 and the comparative example 3, and Ra value (surface roughness). It is a photograph of each conductor of comparative example 3 and examples 1 and 7-12. It is a graph which shows the relationship between content of a component (C) and surface roughness Ra (micrometer) about each conductor of the comparative example 3 and Examples 1, 7-12. It is a graph which shows the relationship between the calcination temperature of each conductive thin film, and specific resistance (ohm * cm). It is a photograph of each conductor of Comparative Example 3 and Examples 14 and 15.

  The conductive composition of the present invention comprises (A) a first organic acid metal salt (hereinafter referred to as component (A)), (B) an aliphatic polyamine, an alicyclic polyamine, and at least one amino group. And at least one amine selected from nitrogen-containing heterocyclic compounds (hereinafter referred to as component (B)), and (C) a metal alkoxide or a second organic acid metal salt (provided that the first organic acid metal salt) And at least one compound selected from the following (hereinafter referred to as component (C)).

The first organic acid metal salt of the component (A) has a solubility increased by the amine of the component (B) and becomes a uniform solution. Therefore, when the conductive composition is applied to the substrate and fired, The metal contained in 1 organic acid metal salt is uniformly stretched to form a thin film, and a conductive film excellent in adhesion to the substrate, surface smoothness and metallic gloss can be formed.
The first organic acid metal salt of component (A) is a metal salt of a fatty acid, and a metal element selected from the group consisting of ruthenium, aluminum, nickel, palladium, platinum, copper, silver, gold, zinc and tin It is preferable that it contains. Examples of the first organic acid metal salt include acetic acid metal salt, formic acid metal salt, oxalic acid metal salt, caprylic acid metal salt, cyclohexanecarboxylic acid metal salt, and cyclohexanepropionic acid metal salt containing the above metal salt.

Specific examples of the first organic acid metal salt of component (A) include palladium acetate, silver acetate, copper acetate, tin acetate, ruthenium acetate, nickel acetate and other acetate metal salts, palladium formate, tin formate, silver formate, Metal formate such as ruthenium formate, palladium oxalate, silver oxalate, copper oxalate, tin oxalate, ruthenium oxalate, nickel oxalate, zinc oxalate and other metal oxalate, nickel caprylate, copper caprylate, Caprylic acid metal salts such as tin caprylate, silver caprylate, palladium caprylate, platinum caprylate, ruthenium caprylate, ruthenium cyclohexanecarboxylate, platinum cyclohexanecarboxylate, platinum cyclohexanecarboxylate, cyclohexanecarboxylate, cyclohexanepropion Examples thereof include ruthenium acid.
Especially, it is preferable that the 1st organic acid metal salt of a component (A) is silver acetate, silver formate, silver oxalate, or silver caprylate.

  The 1st organic acid metal salt of a component (A) may be used individually by 1 type, and may use multiple types together. The organic acid metal salt may be a hydrate.

The component (A) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass with respect to 100% by mass of the total amount of the conductive composition.
When the content of the component (A) in the conductive composition is within the above range, the metal contained in the first organic acid metal salt can be uniformly thinned to form an excellent conductive film. When the component (A) is less than 5% by mass relative to the total amount of the conductive composition, the adhesion of the conductive film to the substrate and the metallic luster may be inferior. The surface smoothness may be inferior.

At least one amine selected from the group consisting of aliphatic polyamines of component (B), alicyclic polyamines and nitrogen-containing heterocyclic compounds having at least one amino group is the first organic component of component (A). Increase the solubility of acid metal salts.
As the component (B) amine, one kind selected from an aliphatic polyamine, an alicyclic polyamine, and a nitrogen-containing heterocyclic compound having at least one amino group may be used alone, or a plurality of kinds may be used in combination. Also good. Among them, it is preferable to select an alicyclic polyamine and / or a nitrogen-containing heterocyclic compound having at least one amino group which is excellent in the effect of increasing the solubility of the first organic acid metal salt of the component (A).

  The aliphatic polyamine of the component (B) is an aliphatic amine having two or more amino groups in the molecule. The aliphatic polyamine includes an aliphatic diamine having two amino groups in the molecule and 3 in the molecule. And an aliphatic triamine having one amino group. Among these, a linear aliphatic diamine having 4 to 8 carbon atoms is preferable.

  Examples of the aliphatic diamine of component (B) include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane and the like. It is done. Among these, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane are preferable.

  The alicyclic polyamine of component (B) is a mono- or polycyclic amine having two or more amino groups and / or aminoalkyl groups as substituents. As the alicyclic polyamine, two amino acids are included in the molecule. A mono- or polycyclic diamine having a group and / or an aminoalkyl group, a mono- or polycyclic triamine having three amino groups and / or an aminoalkyl group in the molecule, and among others, a carbon number of 6 to 12 A monocyclic diamine having an alicyclic skeleton is preferable.

  As the monocyclic diamine of the component (B), 1,2-diaminocyclohexane or 1,3-bis (aminomethyl) cyclohexane is preferable.

  The nitrogen-containing heterocyclic compound having at least one amino group as component (B) may contain an amino group as a ring-constituting atom. On at least one atom constituting the heterocyclic ring, an amino group and / or Alternatively, it may be substituted with an aminoalkyl group. Component (B) is preferably a saturated nitrogen-containing heterocyclic compound containing at least one amino group as a ring constituent atom, and on at least one nitrogen atom as the ring constituent atom, an amino group and More preferably, it is a saturated nitrogen-containing heterocyclic compound substituted with an aminoalkyl group. The aminoalkyl group as a substituent is preferably a group containing a linear or branched alkyl having 1 to 5 carbon atoms.

(B) Nitrogen-containing heterocyclic compounds having at least one amino group include 2-aminomethylpiperidine, 3-aminomethylpiperidine, 4-aminomethylpiperidine, 1- (2-aminoethyl) piperidine, N- ( 2-aminoethyl) piperazine or N, N′-bis (3-aminopropyl) piperazine.
Of these, 1- (2-aminoethyl) piperidine and N- (2-aminoethyl) piperazine, in which at least one nitrogen atom constituting the ring is substituted with an aminoalkyl group, are preferable.

Component (B) is preferably 0.5 to 10.0 mol, more preferably 0.8 to 5.0 mol, and still more preferably 1.2 to 3.0 mol, per 1 mol of component (A). Particularly preferred is 1.5 to 2.0 mol.
When the component (B) is less than 0.5 mol relative to 1 mol of the component (A), the first organic acid metal salt of the component (A) may not be uniformly dissolved. If the component (B) exceeds 10.0 mol with respect to 1 mol of the component (A), the metal content in the conductive composition may be too low to form a good metal film. In addition, the component (B) may inhibit metal sintering during firing.

At least one compound selected from the metal alkoxide of component (C) and the second organic acid metal salt (excluding the organic acid metal salt containing a metal contained in the first organic acid metal salt), At the time of firing, aggregation of the metal contained in the first organic acid metal salt of the component (A) can be suppressed, and adhesion to the substrate, surface smoothness and metal gloss can be improved.
As the compound of component (C), one type selected from metal alkoxides and second organic acid metal salts may be used alone, or a plurality of types may be used in combination.

As the metal alkoxide of the component (C), M (OR) _n (wherein M is a metal element selected from the group consisting of titanium, bismuth, zirconium, aluminum, niobium, silicon, boron, indium and tin, R is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is a valence of the metal element M).

Specific examples of the component (C) metal alkoxide include titanium tetramethoxide (Ti (OCH ₃ ) ₄ ), titanium tetraethoxide (Ti (OC ₂ H ₅ ) ₄ ), titanium tetrapropoxide (Ti (OC _3). H ₇ ) ₄ ), titanium tetrabutoxide (Ti (OC ₄ H ₉ ) ₄ ), zirconium tetramethoxide (Zr (OCH ₃ ) ₄ ), zirconium tetraethoxide (Zr (OC ₂ H ₅ ) ₄ ), zirconi Utetrapropoxide (Zr (OC ₃ H ₇ ) ₄ ), zirconium butoxide (Zr (OC ₄ H ₉ ) ₄ ), aluminum trimethoxide (Al (OCH ₃ ) ₃ ), aluminum triethoxide (Al (OC) ₂ H _{5) 3),} aluminum tripropoxide _{(Al (OC 3 H 7)} 3), aluminum tributoxyethyl _{(Al (OC 4 H 9)} 3), niobium pentane methoxide _{(Nb (OCH 3) 5)} , niobium pentane ethoxide _{(Nb (OC 2 H 5)} 5), niobium pentane propoxide (Nb _(OC 3 _{H 7 5} ), niobium pentambutoxide (Nb (OC ₄ H ₉ ) ₅ ), boron trimethoxide (B (OCH ₃ ) ₃ ), boron triethoxide (B (OC ₂ H ₅ ) ₃ ), boron tri-propoxide (B (OC ₃ H ₇ ) ₃ ), boron tri-normal butoxide (B (OC ₄ H ₉ ) ₃ ), indium trimethoxide (In (OCH ₃ ) ₃ ), indium triethoxide (In (OC ₂ H ₅ ) ₃ ), indium tripropoxide _{(In (OC 3 H 7)} 3), indium butoxide _{(In (OC 4 H 9)} 3), scan Tetramethoxide _{(Sn (OCH 3) 4)} , tin tetraethoxide _{(Sn (OC 2 H 5)} 4), tin tetrapropoxide _{(Sn (OC 3 H 7)} 4), tin tetrabutoxide Doki Sid (Sn (OC ₄ H _{9) 4),} tri-2-ethyl-hexyloxy bismuth, and the like.
Among these, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide or titanium tetranormal butoxide is preferable.

As a 2nd organic acid metal salt of a component (C), it is a C1-C8 fatty acid metal salt, and the thing containing the metal element selected from the group which consists of bismuth, cobalt, titanium, and a zirconium is mentioned.
Specific examples of the second organic acid metal salt include bismuth acetate, cobalt acetate, titanium acetate, zirconium acetate, bismuth octoate, cobalt octoate, titanium octoate, zirconium octoate, and bismuth 2-ethylhexanoate. , Cobalt 2-ethylhexanoate, titanium 2-ethylhexanoate, zirconium 2-ethylhexanoate, etc., among which cobalt 2-ethylhexanoate and bismuth 2-ethylhexanoate are preferable.

The component (C) is preferably contained in an amount of 0.01 to 50 parts by weight, more preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the component (A) in terms of metal.
When the content of component (C) is 0.01 to 50 parts by weight in terms of metal with respect to 100 parts by weight of component (A), the metal contained in component (C) is converted into component (A) during firing. In order to suppress aggregation of the contained metal, it is possible to improve the adhesion to the base material, the surface smoothness and the metallic luster, and to obtain a conductive film having a desired specific resistance value and excellent conductivity. The specific resistance value of the conductive film can be set to a desired specific resistance value by changing the metal content, the firing temperature, etc. contained in the metal alkoxide or the second organic acid metal salt in the conductive composition. An electrically conductive film can be obtained.
For example, a conductive composition having a content of component (C) of 1 part by weight in terms of metal (Ti conversion) is calcined at 300 ° C. with respect to 100 parts by weight of component (A) in terms of metal (Ag conversion). The conductive film obtained has a specific resistance value of about 2.2 × 10 ⁻⁵ Ω · cm, and a conductive composition having a component (C) content of 0.01 part by weight at 300 ° C. The specific resistance value of the conductive film obtained by firing is about 4.7 × 10 ⁻⁶ Ω · cm.

The conductive composition of the present invention may further contain (D) an organic solvent (hereinafter referred to as component (D)).
In the conductive composition of the present invention, by further containing the component (D), the solubility of the organic acid metal salt is increased, and a conductive composition having a smooth and excellent extensibility can be obtained, thereby improving the printability. Thus, a thin and uniform conductive film can be formed.

As the organic solvent of component (D), alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ethers, ether alcohols such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and other ethers, Ol, dihydroterpineol, terpene compounds such as dihydro terpineol acetate.
Of these, methanol, ethanol and the like are preferable.

The above organic solvents may be used alone or in combination of two or more.
Component (D) is preferably 0 to 64 mol, more preferably 1 to 20 mol, and still more preferably 6 to 16 mol, per 1 mol of component (A).

  The conductive composition of the present invention may further contain additives such as a dispersion aid, a surface treatment agent, an antifoaming agent, and a silane coupling agent as necessary.

The conductive composition of the present invention can be prepared, for example, as follows.
The conductive composition of the present invention stirs and mixes the component (A) and the component (B) using a stirring and mixing vessel such as a flask, and uniformly stirs and dissolves the component (D) as necessary. . Add component (C) to the resulting solution and stir for about 15 minutes to 3 hours to prepare a uniform solution. An arbitrary additive may be dissolved in the component (D), or may be dissolved in a mixture in which the components (A), (B), and (C) are dissolved.

  The electrically conductive composition of this invention can be used suitably for formation of conductors, such as an electronic circuit and an electrode, especially the patterned conductor of the base-material surface. In addition, the conductive composition of the present invention can be used as a conductive paste for plating base, a resistance paste, a conductive adhesive, and the like.

The conductor of the present invention has a conductive film formed using a conductive composition.
The conductive film is preferably a thin film having a thickness of 0.1 to 5.0 μm.

  The method for producing a conductor of the present invention includes, for example, a step of applying a conductive composition prepared as described above to a substrate to form a coating film, and a substrate on which the coating film is formed at 150 to 900 ° C. And baking to form a conductive film.

Examples of the substrate include ceramics such as alumina, aluminum nitride, and silicon carbide, resins such as glass, glass-reinforced epoxy resin, polyimide, polyethylene naphthalate, and polyethylene terephthalate.
As a method for forming the coating film, any method such as a method of applying the conductive composition to a substrate or the like using a screen printer, a dispenser, a spin coater or the like can be used.
According to the conductive composition of the present invention, a thin conductive film having a thickness of 0.1 to 5.0 μm can be easily formed without using expensive equipment such as that used in vacuum deposition or sputtering. be able to.

In the step of firing the base material on which the coating film is formed, it is preferable to fire at 150 to 250 ° C. in order to obtain a thin film having excellent adhesion to the base material, surface smoothness and metallic luster. In addition to these characteristics, for example, in order to obtain a conductive thin film excellent in conductivity having a specific resistance value of about 2.2 × 10 ⁻⁵ Ω · cm, baking at 250 to 900 ° C. is preferable.

  The conductive film obtained using the conductive composition of the present invention is not particularly limited, but can be applied to, for example, a plating base film, a resistance film, and the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

Example 1
According to the composition shown in Table 1, component (A) silver acetate and component (B) 1,2-diaminocyclohexane are stirred and mixed, and component (C) titanium tetraisopropoxide and component (D) are mixed. Of ethanol was added, mixed at room temperature for about 2 hours, and stirred to prepare a conductive composition as a uniform solution.
In the conductive composition of Example 1, the component (A) is 19.2% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 3.00 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Example 2)
With the composition shown in Table 1, a conductive composition solution was prepared in the same manner as in Example 1.
In the conductive composition of Example 2, the component (A) is 18.3% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 3.00 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Example 3)
With the composition shown in Table 1, a conductive composition solution was prepared in the same manner as in Example 1.
In the conductive composition of Example 3, the component (A) is 18.7% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 3.00 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

Example 4
With the composition shown in Table 1, a conductive composition solution was prepared in the same manner as in Example 1.
In the conductive composition of Example 4, the component (A) is 18.7% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 3.00 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Example 5)
With the composition shown in Table 1, a conductive composition solution was prepared in the same manner as in Example 1.
In the conductive composition of Example 5, the component (A) is 19.6% by mass relative to 100% by mass of the total composition, and the component (B) is 0.1 mol per component (A). The amount of titanium of component (C) is 3.00 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Comparative Example 1)
(B) Except having used diethanolamine as a component, it carried out similarly to Example 1, and prepared the solution of the conductive resin composition by the composition shown in Table 1.
In the conductive composition of Comparative Example 1, the component (A) is 19.5% by mass with respect to 100% by mass of the total composition, and the diethanolamine is 0.15 with respect to 0.1 mol of the component (A). In terms of metal, the component (C) titanium is 3.00 parts by weight with respect to 100 parts by weight of the component (A) silver.

  The states of the conductive compositions of Examples 1 to 5 and Comparative Example 1 were visually observed. The results are shown in Table 1. In Table 1, ◯ indicates a state in which the solution is solubilized and becomes a uniform solution, and x indicates a non-uniform state in which the solution is not completely dissolved.

  As shown in Table 1, in Examples 1 to 5, the solubility of the component (A) is increased by the component (B), so that it can be completely solubilized and a uniform solution having a smooth and excellent extensibility can be obtained. It was. On the other hand, in Comparative Example 1, the component (A) was not sufficiently dissolved and a uniform solution was not obtained.

(Example 6)
By the composition shown in Table 2, the electroconductive composition was prepared like Example 1-5. In the conductive composition of Example 6, the component (A) is 12.3% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 3.00 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.
Using this conductive composition as a liquid conductive paste, this conductive paste was applied to a slide glass in a pattern of width 10 mm and length 50 mm so as to have a thickness of about 0.05 mm, A conductive thin film having a thickness of 0.2 μm after baking was formed by baking at 500 ° C. for 20 minutes. In addition, the film thickness of the conductive thin film measured the average film thickness using the surface roughness and shape measuring machine (The Tokyo Seimitsu company make, SURFCOM 1500SD2-12).

(Comparative Example 2)
A liquid conductive paste having the composition shown in Table 2 was prepared in the same manner as in Example 6 except that the component (C) was not contained. Using this conductive paste, a conductive thin film having a thickness of 0.2 μm was formed in the same manner as in Example 6.

  About Example 6 and Comparative Example 2, SEM photographs were taken at a magnification of 5000 times using a scanning electron microscope (FE-SEM (JSM-7500F), manufactured by JEOL Ltd.). The results are shown in FIGS.

  As shown in FIG. 1, in the conductor of Example 6, a conductive thin film excellent in surface smoothness and metallic luster was formed. On the other hand, as shown in FIG. 2, the conductor of Comparative Example 2 had a conductive state, but had poor surface smoothness and a porous state in which a large number of holes (concave portions) existed on the surface. .

(Example 7)
A conductive composition was prepared in the same manner as in Example 1 except that the content of component (C) was changed according to the composition shown in Table 3. In the conductive composition of Example 7, the component (A) is 18.7% by mass relative to 100% by mass of the total composition, and the component (B) is 0.1 mol per component (A). It is 0.15 mol, and the titanium of the component (C) is 6.00 parts by weight with respect to 100 parts by weight of the silver of the component (A) in terms of metal.

(Comparative Example 3)
A conductive composition was prepared in the same manner as in Example 1 except that the composition shown in Table 3 did not contain the component (C). In the conductive composition of Comparative Example 3, the component (A) is 19.6% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). 0.15 mol.

  Films after baking in the same manner as in Example 6 except that the conductive compositions of Examples 1 and 7 and Comparative Example 3 were used as conductive paces and the baking temperatures were set at various temperatures shown in Table 3. A conductive thin film having a thickness of 0.5 μm was formed. For the conductor on which the conductive thin film was formed, the surface roughness Ra (arithmetic average roughness) of the conductive thin film was measured by the following method. The results are shown in Table 3 and a graph showing the relationship between the firing temperature and the surface roughness Ra is shown in FIG.

[Measurement method of surface roughness Ra]
In this specification, surface roughness Ra means centerline average roughness (arithmetic average roughness), and surface roughness Ra is based on JIS B 0601 (1994). It was measured using Tokyo Seimitsu make, SURFCOM 1500SD2-12).

  As shown in Table 3 and FIG. 3, the conductive thin film formed using the conductive composition of the present invention is a comparative example whether it is baked at a low temperature of 300 ° C. or baked at a high temperature of 900 ° C. The surface roughness Ra was low and the surface smoothness was excellent.

(Example 8)
A conductive composition was prepared in the same manner as in Example 1 except that the content of component (C) was changed according to the composition shown in Table 4. In the conductive composition of Example 8, the component (A) is 19.6% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). It is 0.15 mol, and the titanium of the component (C) is 0.01 part by weight with respect to 100 parts by weight of the silver of the component (A) in terms of metal.

Example 9
A conductive composition was prepared in the same manner as in Example 1 except that the content of component (C) was changed according to the composition shown in Table 4. In the conductive composition of Example 9, the component (A) is 19.6% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 0.10 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Example 10)
A conductive composition was prepared in the same manner as in Example 1 except that the content of component (C) was changed according to the composition shown in Table 4. In the conductive composition of Example 10, the component (A) is 19.5% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 0.50 part by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Example 11)
A conductive composition was prepared in the same manner as in Example 1 except that the content of component (C) was changed according to the composition shown in Table 4. In the conductive composition of Example 11, the component (A) is 19.5% by mass relative to 100% by mass of the total composition, and the component (B) is 0.1 mol per component (A). The amount of titanium of component (C) is 1 part by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

(Example 12)
A conductive composition was prepared in the same manner as in Example 1 except that the content of component (C) was changed according to the composition shown in Table 4. In the conductive composition of Example 12, the component (A) is 17.9% by mass with respect to 100% by mass of the total composition, and the component (B) is 0.1 mol with respect to 0.1 mol of the component (A). The amount of titanium of component (C) is 12 parts by weight with respect to 100 parts by weight of silver of component (A) in terms of metal.

  The film thickness after baking was 0.5 μm in the same manner as in Example 6 except that the conductive compositions of Examples 1 and 7 to 12 and Comparative Example 3 were used as a conductive paste and burned at 300 ° C. The conductive thin film was formed.

  About each conductor of Examples 1, 7-12, and the comparative example 3, surface roughness Ra (arithmetic mean roughness) of the electrically conductive thin film was measured by said method. Moreover, the specific resistance value of the conductive thin film was measured by the following method. The results are shown in Table 4. In Table 4, ○ indicates that the surface smoothness is excellent and metallic luster is recognized when visually observed, and Δ indicates that the surface smoothness is somewhat excellent and the metallic luster is slightly recognized. X indicates that the surface is porous and has no smoothness, and that no metallic luster is observed.

[Specific resistance measurement method]
The resistance value of each conductive thin film was measured by a 4-terminal method using a 2001 type digital multimeter. Moreover, the film thickness of each conductive thin film was measured with said surface roughness and shape measuring machine. The specific resistance value, for example, indicates 3.2 × 10 ⁻⁶ Ω · cm as “3.2E-06 Ω · cm”.

  The photograph of each conductor of the comparative example 3 and Example 1, 7-12 is shown in FIG. FIG. 5 shows the relationship between the content of the component (C) and the specific resistance value for each conductor. FIG. 6 shows the relationship between the content of the component (C) and the surface roughness Ra (μm) for each conductor.

  As shown in Table 4 and FIG. 4, it was confirmed that Examples 1 and 7 to 12 were excellent in surface smoothness, had a beautiful metallic luster, and reflected light. On the other hand, the conductive thin film of Comparative Example 3 was porous and not excellent in surface smoothness, and the surface was cloudy.

  As shown in Table 4 and FIG. 5, when the content of the component (C) is 0.5 parts by weight or more with respect to 100 parts by weight of the component (A) in terms of metal, the numerical value of the surface roughness (Ra) is It was as low as 0.01 μm or less, and it was confirmed that the surface smoothness was excellent. From this result, it was confirmed that the content of the component (C) was more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the component (A) in terms of metal.

(Example 13)
A conductive composition was prepared in the same manner as in Example 1 except that the content of the component (C) was changed. In the conductive composition of Example 13, the component (C) titanium is 12 parts by weight with respect to 100 parts by weight of the component (A) silver in terms of metal.

  Using the conductive compositions of Examples 1, 7, 10, 13 and Comparative Example 3 as a conductive paste, the firing temperature was 300 ° C, 350 ° C, 400 ° C, 500 ° C, 600 ° C, 700 ° C, 800 ° C, A conductive thin film having a thickness of 0.5 μm after firing was formed in the same manner as in Example 6 except that firing was performed at each temperature of 900 ° C. About these conductors, it carried out similarly to said method, and measured the specific resistance value of the electrically conductive thin film. The results are shown in FIG.

  As shown in FIG. 6, the specific resistance value decreases as the firing temperature increases. However, since the specific resistance value increases as the content of titanium contained in the conductive thin film increases, the content of titanium is preferably lower with respect to 100 parts by weight of component (A) in terms of metal. It could be confirmed. The content of titanium is preferably 20 parts by weight or less with respect to 100 parts by weight of component (A) in terms of metal.

(Example 14)
A conductive composition was prepared in the same manner as in Example 1 except that the component (C) was changed to bismuth 2-ethylhexanoate. In this conductive composition, the bismuth of the component (C) is 2 parts by weight with respect to 100 parts by weight of the silver of the component (A) in terms of metal.

(Example 15)
A conductive composition was prepared in the same manner as in Example 1 except that the component (C) was changed to cobalt 2-ethylhexanoate. In this conductive composition, 2 parts by weight of the cobalt of the component (C) is 100 parts by weight of the silver of the component (A) in terms of metal.

  For each of the conductors of Examples 14 and 15 and Comparative Example 3, the specific resistance value and the surface roughness Ra (arithmetic average roughness) of the conductive thin film were measured by the above method. The results are shown in Table 5. In Table 5, ◯ indicates that the surface smoothness is excellent when visually observed, and x indicates that the surface is porous and has no smoothness.

FIG. 7 shows photographs of the conductors of Examples 14 and 15 and Comparative Example 3.
As shown in Table 5 and FIG. 7, even when bismuth 2-ethylhexanoate (Example 14) and cobalt 2-ethylhexanoate (Example 15) were used as the component (C), surface smoothness was obtained. It was confirmed that an excellent conductive thin film can be formed. On the other hand, the conductive thin film of Comparative Example 3 was a porous film having no surface smoothness.

  The conductive composition of the present invention can form a conductive thin film excellent in adhesion to a substrate, surface smoothness and metallic luster. Although it does not specifically limit as a use which uses the electrically conductive composition of this invention, It can apply to the conductive paste for plating bases, a resistance paste, a conductive adhesive, etc., and is industrially useful. In addition, the conductor of the present invention has a thin and uniform conductive film, and is excellent in adhesion to the base material, surface smoothness and metallic luster of the conductive film. It can be applied to and is industrially useful.

Claims (12)

  (A) a first organic acid metal salt, (B) at least one amine selected from an aliphatic polyamine, an alicyclic polyamine, and a nitrogen-containing heterocyclic compound having at least one amino group, and (C ) A conductive composition comprising a metal alkoxide and a second organic acid metal salt (excluding an organic acid metal salt containing a metal contained in the first organic acid metal salt). object.   The first organic acid metal salt of component (A) is a metal salt of a fatty acid, and a metal element selected from the group consisting of ruthenium, aluminum, nickel, palladium, platinum, copper, silver, gold, zinc and tin The electrically conductive composition of Claim 1 containing.   Component (B) is an aliphatic polyamine which is an aliphatic diamine having 4 to 8 carbon atoms, a monocyclic diamine having an alicyclic skeleton having 6 to 12 carbon atoms having an amino group and / or an aminoalkyl group as a substituent. The alicyclic polyamine, at least one amine selected from nitrogen-containing heterocyclic compounds substituted with at least one nitrogen atom constituting a ring with an amino group or an aminoalkyl group, according to claim 1 or 2. The electroconductive composition as described. The metal alkoxide of component (C) is M (OR) _n (wherein M is a metal element selected from the group consisting of titanium, bismuth, zirconium, aluminum, niobium, silicon, boron, indium and tin, R Is a linear or branched alkyl group having 1 to 10 carbon atoms, and n is a valence of the metal element M), according to any one of claims 1 to 3. Conductive composition.   The electrically conductive composition of Claim 4 whose metal alkoxide of a component (C) is titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, or titanium tetra-n-butoxide.   The second organic acid metal salt of component (C) is a metal salt of a fatty acid having 1 to 8 carbon atoms, and contains a metal element selected from the group consisting of bismuth, cobalt, titanium, and zirconium. 6. The conductive composition according to any one of 5 above.   The electrically conductive composition of any one of Claims 1-6 which contains 5-50 mass% of components (A) with respect to the composition whole quantity.   The electrically conductive composition of any one of Claims 1-7 which contains 0.5-10.0 mol of components (B) with respect to 1 mol of components (A).   The electrically conductive composition of any one of Claims 1-8 which contains 0.01-50 weight part of component (C) with respect to 100 weight part of component (A) in metal conversion.   Furthermore, the electroconductive composition of any one of Claims 1-9 containing the organic solvent of a component (D).   The electrical conductor which has an electrically conductive film obtained using the electrically conductive composition of any one of Claims 1-10.   The process of forming a coating film on a base material using the electrically conductive composition of any one of Claims 1-10, and baking the base material in which the coating film was formed at 150-900 degreeC, and an electrically conductive film A process for producing a conductor, comprising: