KR20080032455A - Anti-migration ink composition and conductive wiring manufactured using the same - Google Patents

Abstract

An anti-migration ink composition is provided to realize excellent conductivity and to inhibit an ion migration phenomenon of conductive interconnections. An anti-migration ink composition comprises: 10-60 wt% of metal nanoparticles formed of silver nanoparticles and copper nanoparticles; and 40-90 wt% of an organic solvent selected from the group consisting of alcohols, polyols and mixtures thereof. The silver nanoparticles and the copper nanoparticles are used in a mixing ratio of 0.001:99.999-50:50. The silver nanoparticles and the copper nanoparticles have a uniform particle size distribution, and each particle size ranges from 3 to 100 nm.

Description

Anti-migration ink composition and conductive wiring manufactured using the same

1 is a diagram schematically showing a mechanism for generating ion migration by metal ions,

2 is a view showing two types of patterns showing a short circuit caused by ion migration.

3 is a view schematically showing a manufacturing process of a migration ink composition according to the present invention,

4 is a FE-SEM picture of the silver nanoparticles obtained in Preparation Example 1,

5 is a FE-SEM picture of the copper nanoparticles obtained in Preparation Example 2,

6 is a view showing a pattern of the PCB accelerated test substrate used in the water drop test,

Figure 7 is a leakage current measurement results with time of the PCB accelerated test substrate according to Examples and Comparative Examples 1 to 3.

The present invention relates to a migration resistant ink composition and a conductive wiring manufactured using the same, and more particularly, to an inkjet ink composition capable of suppressing ion migration in a conductive wiring made of silver and a conductive manufactured using the same. It is about wiring.

As the applicability of nanoscience becomes a reality, efforts to create and transform nanostructures from various angles are rapidly increasing. Nanoparticles, a representative field of nanoscience, have been deeply studied because of their excellent catalytic properties, but recently, there have been many attempts to apply them to printed circuits using printed technology. The reason for using such nanoparticles in Printed Electronics is to make the line width of the wiring used in the electronic component even finer. This is because it is difficult to realize the fine line width when the existing bulk metal particles are applied by the paste method or the plating is used. Therefore, the ultrafine wire width is to be realized using metal nanoparticles having conductivity.

In the case of the implementation of the conductive wiring using the conventional inkjet, mainly silver nano-particles were manufactured by using the conductive ink to form a conductive wiring. There are many reasons why copper, a wiring material used in existing electronic products, is replaced with silver, but mainly because silver is easy to produce nanoparticles and has excellent conductivity.

However, as researches on conductive wirings using silver nanoparticles have been actively conducted, some problems have emerged. Among them, insulation reliability of printed circuit boards due to high density and high integration of electronic components, especially ion-migration, has emerged as the biggest problem.

In ion migration, when an electric field is applied in a state in which moisture such as moisture absorption or condensation is adsorbed between electrodes such as a printer circuit board, metal ions migrate from one metal electrode to the other metal electrode and precipitate a metal or compound. Say the phenomenon. Migration is classified into dendrite and CAF (Conductive Anodic Filament) according to the occurrence type and the occurrence situation. Dendrite refers to a metal or oxide that precipitates on the surface of an insulated part of a printed wiring board, growing in the form of a twig, and shorting the neighboring metal pattern to destroy the insulation between the pattern and the pattern. It refers to a phenomenon in which a metal or an oxide thereof dissolved along an inner glass fiber interface grows into a fibrous structure and destroys insulation between metal patterns.

1 is a diagram schematically showing a mechanism for generating ion migration by metal ions. When electrolysis of water occurs due to the voltage applied to the electrode, oxidation occurs at the anode, and metal ions such as silver and copper are eluted to move toward the cathode in the form of metal ions. Receiving and then metal reduction to grow to a dendrite (dendrite). The grown dendrite causes an electrical short between both electrodes, causing a fatal failure in electronic products such as malfunction of the device or microcomputer.

2 is a view showing two types of patterns showing a short circuit phenomenon by ion migration. One pattern is a form in which hydroxides or oxides precipitate when the metal ions eluted from the positive electrode (anode) are reduced and precipitated near the positive electrode to extend toward the negative electrode (cathode) or when the pH is changed near the negative electrode. The other pattern is a form in which the metal ions eluted from the anode reach the cathode, receive residue from the cathode, precipitate and reduce, and the dendritic phase grows toward the anode.

This migration phenomenon is caused by the narrower line width and line spacing of the wiring, the current flow is suppressed and the environmental factors such as moisture, temperature is added to this. This phenomenon affects the reliability of the product, which greatly lowers the productivity of the product.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is to provide a migration ink composition that can suppress the ion migration phenomenon of the conductive wiring while excellent in conductivity by using a mixture of different types of metal nanoparticles. It is.

Another object of the present invention is to provide a conductive wiring manufactured using the migration ink composition.

In order to solve the above technical problem, in one aspect of the present invention

10 to 60 weight percent of the metal nanoparticles consisting of a mixture of silver nanoparticles and copper nanoparticles; And

40 to 90 weight percent of an organic solvent;

It provides an anti-migration ink composition comprising a.

According to a preferred embodiment, the mixed weight ratio of the copper nanoparticles and silver nanoparticles is preferably 0.001: 99.999 to 50:50.

Here, the silver nanoparticles and the copper nanoparticles preferably have uniform particle distribution with each other. In addition, it is preferable that the particle sizes of the silver nanoparticles and the copper nanoparticles are each independently 3 to 100 nm.

The organic solvent may be composed of an alcohol, a polyol or a mixture thereof. More specific examples include ethanol, methanol, propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, hexanol, octanol, 1,2-hexanediol, diethylene glycol, triethylene glycol, ethylene glycol, propylene glycol , Dipropylene glycol, glycerin, polyethylene glycol, hexylene glycol, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene It is preferably at least one selected from the group consisting of glycol dibutyl ether, ethylene glycol monopropyl ether, dipropylene glycol methyl ether and mixtures thereof.

The silver nanoparticles and copper nanoparticles are preferably used independently of each other prepared in water.

According to a preferred embodiment, the silver nanoparticles comprises the steps of preparing a mixed solution containing a polyol-based organic solvent, capping molecules and a reducing agent; Adding a silver precursor to the mixed solution and reacting by raising the temperature to 70 to 100 ° C; And lowering the temperature of the mixed solution to obtain silver nanoparticles.

Here, the polyol-based organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, butanediol, polyethylene glycol, polypropylene glycol, 1,2- At least one selected from the group consisting of pentanediol and 1,2-hexanediol.

The capping molecule is at least one selected from the group consisting of PVP (Polyvinylpyrrolidone), CTAB (Cetyltrimethylammonium bromide), SDS (Sodium dodecyl sulfate) and Na-CMC (Sodium carboxymethyl cellulose), the capping molecule is 100 parts by weight of the organic solvent It is preferably included in 50 to 120 parts by weight.

The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrazine (N ₂ H ₄ ), sodium hydrophosphate (NaH ₂ PO ₂ ), glucose, ascorbic acid, tannic acid, dimethylformamide, tetrabutylammonium borohydride Ride, sodium borohydride (NaBH ₄ ) and lithium borohydride (LiBH ₄ ) is at least one selected from the group consisting of, the reducing agent is preferably contained in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent. Do.

The silver precursor is AgNO ₃ , AgBF ₄ , AgPF ₆ , Ag ₂ O, CH ₃ COOAg, AgCF ₃ SO ₃ , AgClO ₄ , AgCl, Ag ₂ SO ₄ , CH ₃ COCH = COCH ₃ Ag, Cu (NO ₃ ) ₂ , CuCl ₂ , CuSO ₄ , C ₅ H ₇ CuO ₂ , NiCl ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ , and at least one selected from the group consisting of HAuCl ₄ , the copper precursor is 100 parts by weight of the organic solvent It is preferably included in 0.001 to 50 parts by weight relative to.

According to a preferred embodiment, the step (a) is a step of putting a capping molecule in an organic solvent and stirring at a temperature of 70 to 100 ℃; Cooling the stirred solution to room temperature; And a reducing agent is added to the solution and stirred.

In addition, the reaction time in the step (b) is preferably 10 to 120 minutes.

According to a preferred embodiment, the copper nanoparticles (a) preparing a mixed solution containing a polyol-based organic solvent, capping molecules, a reducing agent and a metal catalyst; (b) adding a copper precursor to the mixed solution and stirring the mixture by raising the temperature to 150 to 180 ° C; And (c) lowering the temperature of the mixed solution to obtain copper nanoparticles.

Here, the polyol-based organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, butanediol, polyethylene glycol, polypropylene glycol, 1,2- At least one selected from the group consisting of pentanediol and 1,2-hexanediol.

The capping molecule is at least one selected from the group consisting of PVP (Polyvinylpyrrolidone), CTAB (Cetyltrimethylammonium bromide), SDS (Sodium dodecyl sulfate) and Na-CMC (Sodium carboxymethyl cellulose), the capping molecule is 100 parts by weight of the organic solvent It is preferably included in 10 to 80 parts by weight.

The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrazine (N ₂ H ₄ ), sodium hydrophosphate (NaH ₂ PO ₂ ), glucose, ascorbic acid, tannic acid, dimethylformamide, tetrabutylammonium borohydride Ride, sodium borohydride (NaBH ₄ ) and lithium borohydride (LiBH ₄ ) is one or more selected from the group consisting of, the reducing agent is preferably included in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent. Do.

The metal catalyst is a metal selected from the group consisting of zinc, iron, tin, lead and aluminum, and the metal catalyst is preferably included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the organic solvent.

The copper precursor is selected from the group consisting of Cu (NO ₃ ) ₂ , CuCl ₂ , CuSO ₄ , (CH ₃ COO) ₂ Cu and C ₅ H ₇ CuO ₂ , wherein the copper precursor is 0.001 based on 100 parts by weight of the organic solvent. It is preferably included to 50 parts by weight.

According to a preferred embodiment, step (a) may be carried out by adding a capping molecule to an organic solvent and stirring at a temperature of 70 to 100 ° C., followed by stirring and adding a metal catalyst and a reducing agent.

In addition, the reaction time in the step (b) is preferably 10 to 120 minutes.

According to a preferred embodiment, in the preparation of the silver nanoparticles and copper nanoparticles, the method of lowering the temperature of the mixed solution is by adding the mixed solution to distilled water, ethylene glycol, alcohol solvent or a mixed solvent of 0 ° C. or less. Can be performed.

Another aspect of the present invention provides a conductive wiring manufactured using the migration ink composition.

Hereinafter, the migration ink composition according to the present invention will be described in more detail.

The ionic migration tendencies of the experimentally presented metals are Ag ⁺ > Pb ²⁺ > Cu ²⁺ > Sn ²⁺ > Au ⁺ , and silver has the greatest tendency to ion migration. In terms of material, there are two ways to suppress ion migration. First, there is a method of wrapping a material that generates a lot of ion migration with a material that generates less ion. Second, there is a method of forming an alloy or mixture with a material that generates less ion migration. In the second method, when alloying the conductive material with the non-conductive material or using a mixture thereof to form the conductive wiring, the use of an alloy or mixture with the non-conductive material is undesirable in that the conductive wiring ultimately prioritizes conductivity. . In addition, the production of heterogeneous metal materials with alloys is not easy to manufacture and there is a problem that the manufacturing cost increases. Accordingly, in the present invention, in consideration of both the ion migration tendency and the conductivity of the metal, by using a mixture of silver and copper, it is possible to minimize the ion migration phenomenon while maintaining high conductivity.

The anti-migration ink composition according to the present invention comprises 10 to 60% by weight of metal nanoparticles consisting of a mixture of silver nanoparticles and copper nanoparticles; And 40 to 90% by weight of an organic solvent consisting of alcohol, polyol or a mixture thereof.

Among the metals, copper has the best electrical conductivity after silver, while silver and copper are theoretically difficult to be eutectic. However, when the nano-sized silver nanoparticles and the copper nanoparticles are dispersed using an organic solvent such as alcohol or polyol as in the present invention, the silver nanoparticles and the copper nanoparticles may not only have dispersibility separately but also each other. It can be uniformly dispersed to maintain uniform conductivity throughout the composition while maintaining high conductivity. Figure 3 schematically shows a process for producing a migration ink composition according to the present invention using silver nanoparticles and copper nanoparticles.

According to a preferred embodiment, the mixed weight ratio of the copper nanoparticles and silver nanoparticles is preferably 0.001: 99.999 to 50:50. If the mixed weight ratio of copper nanoparticles and silver nanoparticles is less than 0.001: 99.999, the migration resistance is not effectively exhibited. If the mixed weight ratio exceeds 50:50, the conductivity is lower than that of silver, and thus the overall conductivity decreases, which is undesirable. .

The silver nanoparticles and the copper nanoparticles preferably have uniform particle distributions. This is because they have a similar particle distribution and are easily dispersed evenly. In addition, the silver nanoparticles and the copper nanoparticles are preferably each independently having a particle size of 3 to 100nm. If the particle size is less than 3nm, it is difficult to synthesize the particles in the water system, and the particle supply price is rapidly increased, which is not preferable.

The organic solvent used in the migration ink composition according to the present invention consists of an alcohol, a polyol or a mixture thereof. Specific examples include ethanol, methanol, propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, hexanol, octanol, 1,2-hexanediol, diethylene glycol, triethylene glycol, ethylene glycol, propylene glycol, Dipropylene glycol, glycerin, polyethylene glycol, hexylene glycol, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol One or more selected from the group consisting of dibutyl ether, ethylene glycol monopropyl ether, dipropylene glycol methyl ether, and mixtures thereof can be used.

The silver nanoparticles and the copper nanoparticles used in the migration ink composition according to the present invention are preferably all synthesized in an aqueous system for dispersibility with the organic solvent. According to a preferred embodiment, the silver nanoparticles and copper nanoparticles may be prepared by the aqueous synthesis method using a polyol solvent, respectively. Hereinafter, a method for preparing the silver nanoparticles and copper nanoparticles using a polyol solvent according to a preferred embodiment will be described in detail.

According to a preferred embodiment, the silver nanoparticles comprises the steps of preparing a mixed solution containing a polyol-based organic solvent, capping molecules and a reducing agent; Adding a silver precursor to the mixed solution and reacting by raising the temperature to 70 to 100 ° C; And lowering the temperature of the mixed solution to obtain silver nanoparticles.

The polyol-based organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, butanediol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol And all kinds of polyhydric alcohols such as 1,2-hexanediol. These can be used individually or in mixture of 2 or more.

The capping molecule is at least one selected from the group consisting of PVP (Polyvinylpyrrolidone), CTAB (Cetyltrimethylammonium bromide), SDS (Sodium dodecyl sulfate) and Na-CMC (Sodium carboxymethyl cellulose), but is not limited thereto. The capping molecule is preferably included in 50 to 120 parts by weight based on 100 parts by weight of the organic solvent. If the content of the capping molecule is less than 50 parts by weight of silver nanoparticles dispersion stability is lowered, if the content is more than 120 parts by weight yield is not increased any more because the manufacturing cost is not preferable.

The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrazine (N ₂ H ₄ ), sodium hydrophosphate (NaH ₂ PO ₂ ), glucose, ascorbic acid, tannic acid, dimethylformamide, tetrabutylammonium borohydride Ride, sodium borohydride (NaBH ₄ ) and lithium borohydride (LiBH ₄ ) is at least one selected from the group consisting of, but is not limited thereto. The reducing agent is preferably included in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent. If the content of the reducing agent is less than 0.001 parts by weight, it is not preferable because the synthesis yield is reduced because all of the metal ions are not reduced. If the content is more than 50 parts by weight, the reaction may explode and the reaction container should be large, which is not preferable.

The silver precursor is AgNO ₃ , AgBF ₄ , AgPF ₆ , Ag ₂ O, CH ₃ COOAg, AgCF ₃ SO ₃ , AgClO ₄ , AgCl, Ag ₂ SO ₄ , CH ₃ COCH = COCH ₃ Ag, Cu (NO ₃ ) ₂ , CuCl ₂ , CuSO ₄ , C ₅ H ₇ CuO ₂ , NiCl ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ , and at least one selected from the group consisting of HAuCl ₄ , but is not limited thereto. The silver precursor is preferably included in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent. If the content of the silver precursor is less than 0.001 parts by weight, it is difficult to form nanoparticles in a desired desired amount. If the content is more than 50 parts by weight, the particle size of the nanoparticles formed is uneven, and the growth rate of the particles is excessively fast, which is undesirable. Can not do it.

According to a preferred embodiment, the preparing step (step a) of the mixed solution, the step of putting a capping molecule in an organic solvent and stirring at a temperature of 70 to 100 ℃; Cooling the stirred solution to room temperature; And a reducing agent is added to the solution and stirred.

It is preferable to add the capping molecule to the organic solvent and stir at a temperature of 70 to 100 ° C. If the temperature is less than 70 ° C. during stirring, the capping molecule is difficult to dissolve, and if the temperature exceeds 100 ° C., the organic solvent may deteriorate. Because it is not desirable. Synthesis of silver nanoparticles is different from the synthesis of copper nanoparticles, by increasing the temperature of the organic solvent containing the capping molecule, stirring, and then cooled to room temperature to add a reducing agent may increase the synthesis yield by optimizing the synthesis of silver nanoparticles.

After the mixture is prepared as described above, the silver precursor is added to the mixed solution and the mixture is heated and stirred at a temperature of 70 to 100 ° C. (step b) is not preferable because the yield is low when the temperature is lower than 70 ° C. after the precursor is added. When the temperature rises above 100 degreeC, since particle growth is fast, it is unpreferable. Stir for 10 to 120 minutes while raising the temperature. If the reaction time is less than 10 minutes, silver ions are difficult to be reduced sufficiently, and if it exceeds 120 minutes, silver nanoparticles grow excessively, which is not preferable.

When the reaction of the mixture proceeds to form nuclei of particles and grow into nanoparticles of a desired size, the temperature of the mixture is lowered to obtain nanoparticles. (step c)

In the method of lowering the temperature of the mixed liquid, the temperature can be lowered by cooling distilled water, ethylene glycol, an alcohol solvent, a mixed solvent thereof, or the like to 0 ° C. or lower, and adding the mixed liquid thereto. In this way, the size of the nanoparticles can be controlled by drastically reducing the reaction temperature.

Obtaining the nanoparticles may be performed by precipitating the nanoparticles by adding an excess of a nonpolar solvent to the mixture. Specifically, for example, acetone may be used as the nonpolar solvent. According to a preferred embodiment of the present invention, the amount of the nonpolar solvent to be added is preferably 200 to 300 parts by weight based on 100 parts by weight of the total weight of the solution of the previous step. As such, when an excessive amount of the nonpolar solvent is added to the mixed solution, the nanoparticles dispersed in an organic solvent such as ethylene glycol sink and mix with the nonpolar solvent due to the difference in solubility.

The nanoparticles thus precipitated can be separated from the mixed solution by centrifuging the mixed solution. Centrifugation may be performed at 2,000 to 4,000 rpm for 1 minute to 10 minutes.

The nanoparticles thus obtained can be obtained in the form of powder of several tens of nanometers by washing with an organic solvent and drying.

The washing process may be performed by repeatedly washing the nanoparticles using distilled water and a nonpolar solvent as an organic solvent, and the drying process may be performed in any one of a vacuum oven, an electric furnace or a dryer. Here, the drying process is preferably carried out at 30 to 60 ℃ temperature under nitrogen or air atmosphere.

On the other hand, copper nanoparticles can be prepared by the following process.

According to a preferred embodiment, the copper nanoparticles comprises the steps of: (a) preparing a mixed solution comprising a polyol-based organic solvent, a capping molecule, a reducing agent and a metal catalyst; (b) adding a copper precursor to the mixed solution and stirring the mixture by heating it to a temperature of 150 to 180 ° C; And (c) lowering the temperature of the mixed solution to obtain copper nanoparticles.

Polyol-based organic solvents, capping molecules, and reducing agents used in the production of copper nanoparticles may be the same as those used in the production of the silver nanoparticles.

However, the content of the capping molecule is preferably included in 10 to 80 parts by weight based on 100 parts by weight of the organic solvent. If the content of the capping molecule is less than 10 parts by weight, the metal particles may be unevenly grown beyond the nano-size, the dispersion stability of the nanoparticles are inferior, and if the content exceeds 80 parts by weight, the yield does not increase any more, so the manufacturing cost is high. I can't.

The reducing agent is preferably included in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent. If the content of the reducing agent is less than 0.001 parts by weight, it is not preferable because the synthesis yield is reduced because all of the metal ions are not reduced. If the content is more than 50 parts by weight, the reaction may explode and the reaction container should be large, which is not preferable.

Unlike the silver nanoparticles, copper nanoparticles may be prepared using a metal powder selected from the group consisting of zinc, iron, tin, lead, and aluminum as metal catalysts. For copper, the standard reduction potential is 0.24V, so standard reduction potentials such as zinc (-0.76V), iron (-0.02V), tin (-0.14V), lead (-0.16V), aluminum (-1.66V) When a low metal is used as a catalyst, these catalysts can effectively reduce + divalent copper ions to zero-valent copper as they are oxidized. This makes it possible to synthesize a high concentration of aqueous nanoparticles. The oxidized metal catalyst serves as a catalyst in the final mechanism by being oxidized again by the process of oxidizing the organic solvent and the like and by the electrons generated in the excess reducing agent that does not participate in the reaction. In this way, copper nanoparticles can be produced in a high yield when using a metal catalyst, and precipitation can not be made even under centrifugation of 3000 rpm or more, and in the stationary phase, copper nanoparticles can be prepared that remain dispersed in a solution phase for more than a full time. .

The metal catalyst is preferably contained in 0.01 to 50 parts by weight based on 100 parts by weight of the organic solvent. If the content of the metal catalyst is less than 0.01 parts by weight, the amount of nanoparticles that can be obtained is not preferable because it is small, and if the content exceeds 50 parts by weight, the size of the nanoparticles is not uniform, which is not preferable.

The copper precursor may use a compound containing copper, such as a compound such as Cu (NO ₃ ) ₂ , CuCl ₂ , CuSO ₄ , (CH ₃ COO) ₂ Cu, C ₅ H ₇ CuO ₂ , and the like. no. The content of the copper precursor is preferably included in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent. If the content of the copper precursor is less than 0.001 parts by weight, it is difficult to form nanoparticles in a desired desired amount. If the content is more than 50 parts by weight, the particle size of the formed nanoparticles is uneven, and the growth rate of the particles is excessively fast, which is undesirable. Can not do it.

According to a preferred embodiment, the step (a) of preparing the mixed solution may be performed by adding a capping molecule to an organic solvent and stirring at a temperature of 70 to 100 ° C., followed by stirring and adding a metal catalyst and a reducing agent. If the temperature is less than 70 ° C. during stirring, the capping molecules are hardly dissolved, and if the temperature is more than 100 ° C. during stirring, the solvent may deteriorate, which is not preferable.

After the mixed solution is prepared, a copper precursor is added to the mixed solution, and the mixture is heated to a predetermined temperature and stirred. (Step b) In this step, the oxidation state of the copper nanoparticles is determined by adjusting the temperature at the time of raising the temperature. Likewise, when synthesizing copper nanoparticles having an oxidation state of 0, the temperature of the mixed solution is preferably increased to 150 to 180 ° C. This is because when the polyol-based aqueous solvent is used, the reaction rate is low when the temperature is lower than 150 ° C., thereby obtaining copper oxide nanoparticles. When the temperature is higher than 180 ° C., the organic solvent is vaporized, which is not preferable. . Stir for 10 to 120 minutes while raising the temperature. If the reaction time is less than 10 minutes, it is difficult to sufficiently reduce the copper ions, and if it exceeds 120 minutes, the copper nanoparticles are excessively grown and it is difficult to control the particle size.

The copper nanoparticles thus formed may be obtained through washing and separation processes in the same manner as in the obtaining of the silver nanoparticles.

Hereinafter, the present invention will be illustrated by the following examples, but the protection scope of the present invention is not limited only to the following examples.

Preparation Example 1 Synthesis of Silver Nanoparticles

200 g of ethylene glycol and 200 g of PVP having a molecular weight of 10,000 were added to a three-neck 1 L round flask, and the mixture was stirred at 90 ° C. to uniformly dissolve. The solution was cooled to room temperature again. 10 g of glucose was added thereto and stirred. Then 40g of silver nitrate (silver nitrate) was added and the temperature was raised to 4 ° C. per minute and reacted at 90 ° C. for 30 minutes. After completion of the reaction, the reaction solution was poured into 200 g of distilled water to lower the temperature, and 400 ml of acetone was added thereto to precipitate the silver nanoparticles. The solution was centrifuged at 4000 rpm for 5 minutes to separate the silver nanoparticles from the solution, washed three times with distilled water and acetone in the same manner, and dried in a vacuum oven at 45 ° C. to obtain powdered silver nanoparticles.

Preparation Example 2 Synthesis of Copper Nanoparticles

500 g of ethylene glycol and 200 g of PVP having a molecular weight of 10,000 were added to a 3-necked 1 L round flask, and the mixture was stirred at 90 ° C. and uniformly dissolved. 2 g of zinc (Zn) powder, 5 g of NaOH, and 10 g of glucose were added thereto and stirred. Then 40 g of copper sulfate pentahydrate was added thereto and stirred at 170 ° C. for 30 minutes. After completion of the reaction, the reaction solution was poured into 500 g of distilled water to lower the temperature, and 1 L of acetone was added thereto to precipitate copper oxide nanoparticles. The solution was centrifuged at 4000 rpm for 5 minutes to separate the copper oxide nanoparticles from the solution, washed three times with distilled water and acetone in the same way, and dried in a vacuum oven at 45 ° C (9g, 90% yield). ) Was prepared.

FE-SEM images of the silver nanoparticles and the copper nanoparticles obtained in Preparation Examples 1 and 2 are shown in FIGS. 4 and 5, respectively. 4 and 5, it can be seen that each nanoparticle has a size of 30 ~ 50nm. In addition, they are easily synthesized in an aqueous system and easily dissolved in an aqueous solvent, and are excellent in dispersion stability after melting.

<Example>

The mixed weight ratio of the copper nanoparticles obtained in Preparation Example 2 and the silver nanoparticles obtained in Preparation Example 1 was weighed and mixed at 5:95, and 20 wt% of the mixed nanoparticles was 80 wt% of diethylene glycol monobutyl ether. It was dissolved in% to prepare a migration ink composition.

Comparative Example 1

An ink composition was prepared in the same manner as in the above example, except that only silver nanoparticles were used as 100%.

Comparative Example 2

An ink composition was prepared in the same manner as in the above example, except that the silver nanoparticles and the palladium nanoparticles were mixed at 90:10.

Comparative Example 3

An ink composition was prepared in the same manner as in the above example, except that silver nanoparticles and palladium nanoparticles were mixed at 80:20.

Water drop test was performed to evaluate the ion migration of the ink compositions prepared in Examples and Comparative Examples 1 to 3. The PCB accelerated test substrate model used for the test is shown in FIG. 6. As in the shape of the pattern shown in Figure 6, using the ink composition prepared in the above Examples and Comparative Examples 1 to 3 to prepare a PCB accelerated test substrate having a pattern width of 1.5mm, the gap between the pattern and the pattern 1.5mm It was.

1) Test conditions: in air, 15V, distilled water drops, max. 1.5mA

2) Evaluation method: measuring the sensitivity of electrochemical migration by high acceleration test, and measuring the leakage current as the dendrite grows under the distilled water drop and 15V bias.

The leakage current with time of the PCB acceleration test substrate used in the water drop test was measured and shown in FIG. 7. As shown in Figure 7, it can be seen that when using the ink composition according to the invention the leakage current over time showed a constant low value. Comparative Example 3 can be compared with Example 1, but is not preferred because palladium is expensive. After 10 minutes, the leakage current amount is as shown in Table 1 below. As a result, the migration ink composition according to the present invention can be seen that dendrite growth is suppressed, so that the leakage current shows a relatively low value.

TABLE 1

Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Leakage current amount at 10 minutes (unit: 10 ^-4 A) 0.777 5.40 6.47 2.17

The present invention is not limited to the above embodiments, and many variations are possible by those skilled in the art within the spirit of the present invention.

As described above, according to the anti-migration ink composition according to the present invention, the ion migration phenomenon can be effectively suppressed in the conductive wiring made of silver without lowering the conductivity.

Claims (23)

10 to 60 weight percent of the metal nanoparticles consisting of a mixture of silver nanoparticles and copper nanoparticles; And 40 to 90% by weight of an organic solvent consisting of an alcohol, a polyol or a mixture thereof; An anti-migration ink composition comprising a. The method of claim 1, The mixed weight ratio of the copper nanoparticles and silver nanoparticles is 0.001: 99.999 to 50:50 migration ink composition. The method of claim 1, The silver nanoparticles and the copper nanoparticles are a migration ink composition having a uniform particle distribution. The method of claim 1, Particle sizes of the silver nanoparticles and the copper nanoparticles are independently migration ink composition of 3 to 100nm. The method of claim 1, The organic solvent is ethanol, methanol, propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, hexanol, octanol, 1,2-hexanediol, diethylene glycol, triethylene glycol, ethylene glycol, propylene glycol, Dipropylene glycol, glycerin, polyethylene glycol, hexylene glycol, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol A migration ink composition, wherein the migration ink composition is at least one selected from the group consisting of dibutyl ether, ethylene glycol monopropyl ether, dipropylene glycol methyl ether, and mixtures thereof. The method of claim 1, The silver nanoparticles and copper nanoparticles are each independently prepared in a water-based migration ink composition. The method of claim 1, The silver nanoparticles are Preparing a mixed solution containing a polyol-based organic solvent, a capping molecule, and a reducing agent; Adding a silver precursor to the mixed solution and reacting by raising the temperature to 70 to 100 ° C; And Lowering the temperature of the mixed solution to obtain silver nanoparticles; Migration ink composition prepared by a manufacturing method comprising a. The method of claim 7, wherein The polyol-based organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, butanediol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol And at least one selected from the group consisting of 1,2-hexanediol. The method of claim 7, wherein The capping molecule is at least one selected from the group consisting of PVP (Polyvinylpyrrolidone), CTAB (Cetyltrimethylammonium bromide), SDS (Sodium dodecyl sulfate) and Na-CMC (Sodium carboxymethyl cellulose), the capping molecule is 100 parts by weight of the organic solvent Migrating ink composition comprising 50 to 120 parts by weight with respect to. The method of claim 7, wherein The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrazine (N ₂ H ₄ ), sodium hydrophosphate (NaH ₂ PO ₂ ), glucose, ascorbic acid, tannic acid, dimethylformamide, tetrabutylammonium borohydride Hydride, sodium borohydride (NaBH ₄ ) and lithium borohydride (LiBH ₄ ) is at least one selected from the group consisting of, the reducing agent is migration resistant to 0.001 to 50 parts by weight based on 100 parts by weight of an organic solvent Ink composition. The method of claim 7, wherein The silver precursor is AgNO ₃ , AgBF ₄ , AgPF ₆ , Ag ₂ O, CH ₃ COOAg, AgCF ₃ SO ₃ , AgClO ₄ , AgCl, Ag ₂ SO ₄ , CH ₃ COCH = COCH ₃ Ag, Cu (NO ₃ ) ₂ , CuCl ₂ , CuSO ₄ , C ₅ H ₇ CuO ₂ , NiCl ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ , and at least one selected from the group consisting of HAuCl ₄ , the copper precursor is 100 parts by weight of the organic solvent Migrating ink composition contained in an amount of 0.001 to 50 parts by weight. The method of claim 7, wherein Step (a) is a step of putting a capping molecule in an organic solvent and stirring at a temperature of 70 to 100 ℃; Cooling the stirred solution to room temperature; And adding a reducing agent to the solution and stirring the migration ink composition. The method of claim 7, wherein The migration ink composition of step (b) the reaction time is 10 to 120 minutes. The method of claim 1, The copper nanoparticles are (a) preparing a mixed solution including a polyol-based organic solvent, a capping molecule, a reducing agent, and a metal catalyst; (b) adding a copper precursor to the mixed solution and stirring the mixture by raising the temperature to 150 to 180 ° C; And (c) lowering the temperature of the mixed solution to obtain copper nanoparticles; Migration ink composition prepared by a manufacturing method comprising a. The method of claim 14, The polyol-based organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, butanediol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol And at least one selected from the group consisting of 1,2-hexanediol. The method of claim 14, The capping molecule is at least one selected from the group consisting of PVP (Polyvinylpyrrolidone), CTAB (Cetyltrimethylammonium bromide), SDS (Sodium dodecyl sulfate) and Na-CMC (Sodium carboxymethyl cellulose), the capping molecule is 100 parts by weight of the organic solvent Migration ink composition contained in 10 to 80 parts by weight relative to. The method of claim 14, The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrazine (N ₂ H ₄ ), sodium hydrophosphate (NaH ₂ PO ₂ ), glucose, ascorbic acid, tannic acid, dimethylformamide, tetrabutylammonium borohydride Hydride, sodium borohydride (NaBH ₄ ) and lithium borohydride (LiBH ₄ ) is at least one selected from the group consisting of, the reducing agent is migration is included in 0.001 to 50 parts by weight based on 100 parts by weight of the organic solvent Ink composition. The method of claim 14, The metal catalyst is a metal selected from the group consisting of zinc, iron, tin, lead and aluminum, the metal catalyst is a migration ink composition comprising 0.01 to 50 parts by weight based on 100 parts by weight of an organic solvent. The method of claim 14, The copper precursor is selected from the group consisting of Cu (NO ₃ ) ₂ , CuCl ₂ , CuSO ₄ , (CH ₃ COO) ₂ Cu and C ₅ H ₇ CuO ₂ , wherein the copper precursor is 0.001 based on 100 parts by weight of the organic solvent. Migration ink composition comprising from 50 parts by weight. The method of claim 14, The step (a) is a method for producing metal nanoparticles carried out by adding a capping molecule to an organic solvent and stirring at a temperature of 70 to 100 ℃, and a metal catalyst and a reducing agent. The method of claim 14, In the step (b), the stirring time is 10 to 120 minutes. The method according to claim 7 or 14, The method of lowering the temperature of the mixed liquid in the step (c) is a migration ink composition carried out by adding the mixed liquid to distilled water, ethylene glycol, alcohol solvent or a mixed solvent of 0 ℃ or less. A conductive wiring manufactured using the migration ink composition according to claim 1.

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