KR20160101383A - multistep light sintering method of copper nano ink and patterned copper nanoink thereby - Google Patents

Abstract

The present invention relates to a multi-step light sintering method of a copper nanoink, which includes treating the surface of a substrate with plasma before light sintering, and incorporating an adhesive material, such as silane and epoxy, to the copper nanoink to improve the binding force between the substrate and the copper nanoink, uses multi-step light sintering and a complex light source to reduce the interfacial resistance on the contact surface between the substrate and the ink, and can provide a patterned copper nanoink having improved adhesion, fatigue property and bending property. In addition, when a copper nanoink is patterned by using the multi-step light sintering according to the present invention, it is possible to pattern the ink in a short time within several seconds at room temperature under ambient condition with no damage on a polymer substrate, and to accomplish mass production by virtue of a simple and easy process. Further, the multi-step light sintering method of a copper nanoink and the patterned copper nanoink can be applied in various industrial fields, including a flexible electronic product, large-area display, thin film type solar cell, touch screen panel, thin film transistor (TFT) device, or the like.

Description

A multi-light sintering method of copper nano ink and a patterned copper nano ink using the same,

The present invention relates to a multi-photo-sintering method of copper nano ink and a patterned copper nano ink using the same, more particularly, to a multi-photo- The present invention relates to a multi-photo-sintering method of nano-ink and a patterned copper nano ink using the same.

Recently, with the development of electronic engineering and information technology, demand for portable electronic devices is steadily increasing. In general, portable electronic devices are manufactured through a photolithography process, which involves complicated processes of 12 or more steps, and requires a long manufacturing time, which causes a problem of consuming a large amount of money.

Therefore, in order to solve the above-mentioned problems, a total of three printing electronic technologies have been developed in which a conductive ink containing metal nanoparticles in a dispersion medium is prepared, printed on a substrate, dried and sintered. This is more advantageous than the conventional photolithography process because it is environmentally friendly and can mass-produce a large area without deteriorating the flexibility of the pattern.

However, current conductive inks use gold, silver and copper nanoparticles. In order to sinter the conductive ink, a thermal sintering method, generally performed at 300 ° C or higher, is used. When applied to a flexible substrate , A dense thin film having a crystalline structure is formed and cracks are generated, which is disadvantageous in that it is not suitable for a flexible substrate using a polymer series which has recently been attracting attention. In addition, since it involves a long process through a subsequent heat treatment process, the process has a complicated process.

On the other hand, laser sintering, plasma sintering and microwave sintering methods have been proposed. However, since the pattern bonding is not completely performed, the polymer substrate (flexible substrate) which has high sheet resistance, low melting point, There is a disadvantage in that it can not be used, the adhesion characteristic of the produced pattern and the durability against repetitive bending are low, which is not suitable for mass production.

On the contrary, when the conductive ink is simply applied and then the light sintering which converts the light energy into thermal energy by an optical method is used, sintering is possible in a short time, so that it is advantageous in mass production. However, this also causes shrinkage of the polymer substrate (flexible substrate) and conductive ink, and there is a problem that the produced pattern has low adhesion property, durability and reliability.

Therefore, in order to pattern a conductive ink on a flexible substrate utilizing a polymer material, a method of sintering copper nano ink capable of sintering in a very short time under normal atmospheric conditions without affecting other components through chemical reaction It is necessary to develop.

Patent Document 1. Korean Patent Laid-Open No. 10-2012-0132424

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide an ink jet recording head capable of improving the adhesion between a substrate and a copper nano ink during patterning of copper nano ink and excellent durability and reliability And a method for sintering multiple copper nanoinks.

Another object of the present invention is to provide a patterned copper nanoink with excellent adhesion to a substrate, durability and reliability.

In order to accomplish the above object, the present invention provides a multi-light sintering method of copper nano ink comprising the steps of:

(I) treating the substrate surface with oxygen plasma or ozone gas,

II) 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of a solvent; and 50 to 160 parts by weight of a copper nanoparticle or a mixture of copper nanoparticles and a precursor; And 3 to 10 parts by weight of a polymeric binder resin;

III) patterning the copper nano ink on the surface-treated substrate,

Drying the patterned copper nano ink at 70 to 150 캜,

V) a step of first photo-sintering by irradiating a Xenon lamp after drying;

VI) a second photo-sintering step of irradiating the photo-sintered copper nano ink with a deep ultraviolet (UV) lamp and a xenon lamp.

The solvent may be selected from the group consisting of 2-butoxy ethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol butyl ether, cyclohexanone, cyclohexanol, 2-ethoxyethyl acetate, ethylene glycol diacetate, Terpineol, isobutyl alcohol, and a mixed solution thereof.

The mixture of the copper nanoparticles and the copper precursor may be mixed in a ratio of 10 to 40 parts by weight of the copper precursor to 100 parts by weight of the copper nanoparticles.

The polymeric binder resin may be selected from the group consisting of hydroxypropylmethylcellulose (HPMC), polyurethane dispersions (PUD), polyurethane diols, polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, Acrylate, acrylate, acrylate, acrylate, acrylate,

The solvent may be selected from the group consisting of 2-butoxy ethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol butyl ether, cyclohexanone, cyclohexanol, 2-ethoxyethyl acetate, ethylene glycol diacetate, Terpineol, isobutyl alcohol, and a mixed solution thereof.

The mixture of the copper nanoparticles and the copper precursor may be mixed in a ratio of 10 to 40 parts by weight of the copper precursor to 100 parts by weight of the copper nanoparticles.

The polymeric binder resin may be selected from the group consisting of hydroxypropylmethylcellulose (HPMC), polyurethane dispersions (PUD), polyurethane diols, polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, Acrylate, acrylate, acrylate, acrylate, acrylate, acrylate,

The average diameter of the copper nanoparticles is 5 to 100 nm and the copper precursor is CuCl 2, Cu (acac) 2, Cu (tfac) ₂, Cu (tfac) Selected from the group consisting of Cu (fod) ₂, Cu (acim) ₂, Cu (nona-F) ₂, Cu (acen) ₂, Cu (NO ₃ ) ₂揃 3H ₂ O or CuSO ₄揃 5H ₂ O Or more.

Wherein the adhesion promoter is selected from the group consisting of an acrylic resin, an olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic acid resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, an epoxy resin, an epoxy silane, a monosilane, a trimethoxysilane and a polyimide resin And the like.

The patterning step may be performed by screen printing, inkjet printing, gravuring, bar coater, or spraying method.

The first light sintering step may be 0.5 to 2.0 ms, the pulse gap may be 20 to 30 ms, the number of pulses may be 15 to 30, and the intensity of light may be 5 to 15 J / cm 2.

In the second light sintering step, the pulse width of the xenon lamp is 0.1 to 5 ms, the pulse number is once, the intensity of light is 5 to 10 J / cm 2, (UV) lamp may be irradiated for 0 to 300 seconds at 0 to 100 mW / cm < 2 >.

According to another aspect of the present invention, there is provided a copper nano-ink comprising: 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of a solvent; and 50 to 160 parts by weight of copper nanoparticles or copper nanoparticles and a precursor mixture; And 3 to 10 parts by weight of a polymeric binder resin, wherein the adhesion promoter is selected from the group consisting of an acrylic resin, a chlorinated olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, Wherein the copper nano ink may be any one selected from the group consisting of an epoxy silane, a monosilane, a trimethoxysilane, and a polyimide resin, and the copper nano ink is patterned through multiple light sintering Lt; / RTI >

Wherein the first light sintering step comprises the steps of: 0.5 to 2.0 ms; the pulse gap is 20 to 30 ms; the number of pulses is 15 to 30; the intensity of light 5 to 15 J / cm < 2 >.

In the second light sintering step, the pulse width of the xenon lamp is 0.1 to 5 ms, the pulse number is once, the intensity of light is 5 to 10 J / cm 2, (UV) lamp may be irradiated for 0 to 300 seconds at 0 to 100 mW / cm < 2 >.

In the multi-photo-sintering method of the copper nano ink of the present invention, the surface of the substrate is subjected to a plasma treatment before photo-sintering, and an adhesion material such as silane and epoxy is contained in the copper nano ink to improve the bonding force between the substrate and the copper nano- It is possible to provide a patterned copper nano ink having improved adhesion, fatigue property, and bending property, which can lower the interface resistance between the substrate and the ink contact surface by using multiple light sintering and compound light sources.

In addition, patterning the copper nano ink using the multi-light sintering method of the present invention can pattern the ink in a short time within a few seconds under normal atmospheric conditions without damaging the polymer substrate, and since the process is simple and easy, .

In addition, the multi-photo-sintering method and the patterned copper nano ink of the copper nano ink can be applied variously to a flexible electronic product, a large area display, a thin plate solar cell, a touch screen panel, a thin film transistor (TFT) Do.

1 is a process flow diagram illustrating a multi-photo-sintering method of copper nanoink according to an embodiment of the present invention.
2 is a view showing a conventional photo-sintering method of copper nano ink and a multi-photo-sintering method according to an embodiment of the present invention.
FIG. 3 is a conceptual view illustrating a mechanism for improving the adhesion of copper nano ink under the multiple light sintering conditions according to the present invention.
4 is a diagram illustrating a process of patterning a nano ink by receiving light energy by a composite light source according to an embodiment of the present invention.
5 is a graph showing the sheet resistance of the patterned copper nano ink prepared according to Examples 1 to 7 of the present invention.
Fig. 6 is an electron micrograph of the patterned copper nano ink prepared from Example 1 of the present invention before photo-sintering, after the first photo-sintering step and after the second photo-sintering step.
Fig. 7 is a photograph comparing the adhesion characteristics of the patterned copper nanoinks prepared in Example 5, Example 6, and Example 7 of the present invention.
8 is a photograph showing the flexural characteristics of the patterned copper nano ink prepared from Example 1 of the present invention and Comparative Example 1 and Comparative Example 5. Fig.
FIG. 9 is a graph showing the resistance change of the patterned copper nano ink when repeatedly bending tests of the patterned copper nanoinks prepared in Comparative Examples 5 and 6, which are single sided light sintering methods, are performed .
FIG. 10 shows the results of the repeated outward bending tests of the patterned copper nanoinks prepared in Example 1, Example 5, Example 6, and Example 8, which are multistage optical sintering methods, This graph is a graph measuring the resistance change of nano ink.
11 is a graph showing the sheet resistance of the patterned copper nano ink prepared in Comparative Examples 1 to 4 of the present invention.
Fig. 12 is a photograph showing the adhesive force characteristics of the patterned copper nano ink prepared in Comparative Examples 1 to 4 of the present invention.

Hereinafter, the present invention will be described in more detail.

Conventionally, high temperature (200 to 350 ° C) heat, laser and chemical methods have been used in the inert gas to photo-sinter the copper nano ink. This method consumes a lot of time and has a low melting point, But it can not be used in a polymer substrate which can be caused.

Therefore, in order to solve the above problems, a light sintering method capable of sintering in a very short time under atmospheric conditions without room damage has been developed. However, when patterning is performed through a single light sintering process, Or the patterned copper nano ink contracts and warps, and the adhesive force with the substrate is weak, so that peeling may occur between the patterned ink and the interface between the substrate and the substrate.

In order to solve the above problems,

(I) treating the substrate surface with oxygen plasma or ozone gas,

II) 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of a solvent; and 50 to 160 parts by weight of a copper nanoparticle or a mixture of copper nanoparticles and a precursor; And 3 to 10 parts by weight of a polymeric binder resin;

III) patterning the copper nano ink on the surface-treated substrate,

Drying the patterned copper nano ink at 70 to 150 캜,

V) a step of first photo-sintering by irradiating a Xenon lamp after drying, and

(VI) a second photo-sintering step of irradiating the photo-sintered copper nano ink with a deep ultraviolet (UV) lamp and a xenon lamp.

As shown in Fig. 1, first, in the step (I), the substrate surface is treated with oxygen plasma or ozone gas as described above. The surface of the substrate may be placed in a chamber capable of generating an oxygen plasma or an ozone gas atmosphere, or a portion to be surface-treated may be placed on the bottom of a device capable of generating plasma or ozone gas, .

At this time, if the surface of the substrate is treated with plasma, C-C and C-H bonding are cut off and removed, and a hydroxyl group is generated on the surface. When the functional group is a hydroxyl group, the copper nano ink of the present invention is particularly easy and can be strongly bonded.

3, the hydroxyl groups exposed on the surface of the substrate and the functional groups such as methoxy, ethoxy, and acetoxy contained in the copper nano ink are combined with the hydroxyl groups, So that the substrate and the film can be strongly adhered to each other.

In order to bring the substrate into an activated state (an exposed state of a hydroxyl group), energy must be applied. In the present invention, a method of applying plasma energy to a substrate and a method of contacting ozone gas may be used.

If ultraviolet rays are used in addition to plasma or ozone gas, the organic CC and CH are cut and removed in the thickness direction as a whole, so that inorganicization proceeds and the flexibility of the substrate due to the presence of organic components is totally lowered, There is a problem that the time required for the operation is long.

Therefore, it is preferable to treat with plasma or ozone gas because it is possible to selectively cut only a part of molecular bonds of the material constituting the substrate in the vicinity of the substrate surface.

The substrate may be selected from the group consisting of polyimide film (PI), bismaleimide triazine (BT) and a combination of epoxy resin and glass fiber, polyethylene film (PE), polyethylene terephthalate (PET) have.

Ii) 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of the solvent; and 50 to 160 parts by weight of a mixture of copper nanoparticles or copper nanoparticles and a precursor; And 3 to 10 parts by weight of a polymeric binder resin.

The polymer binder resin contained in the copper nano ink improves the dispersibility of the ink during the production of the copper nano ink and acts as a reducing agent to remove the oxide film of the copper nanoparticles upon sintering to lower the resistance after sintering And as a result, it is possible to provide a patterned copper electrode pattern with improved electrical conductivity. In addition, the polymeric binder resin contained in the copper nano ink is preferably contained in an amount of 3 to 10 parts by weight based on 100 parts by weight of the solvent of the copper nano ink. When the content of the polymeric binder resin is less than the lower limit of 3 parts by weight, the oxide film of the copper nanoparticles can not be completely removed at the time of sintering, so that the electrical conductivity is lowered after sintering. If the content is higher than the upper limit of 10 parts by weight, The binder resin may interfere with the sintering of the copper nanoparticles and the precursor, and it may be difficult to lower the electric conductivity.

The polymeric binder resin may be, for example, selected from the group consisting of hydroxypropylmethylcellulose (HPMC), polyurethane dispersion (PUD), polyurethane diol, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polymethyl Methacrylate, dextran, or mixtures thereof.

In addition, for ease of use of the copper nano ink, a solvent may be included. The solvent may be, for example, 2-butoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol butyl ether, cyclohexanone, cyclohexanol, 2- ethoxyethyl acetate, ethylene Glycol diacetate, terpineol, isobutyl alcohol, and a mixed solution thereof.

The copper nanoparticles and the copper precursor may be mixed in a ratio of 10 to 40 parts by weight of the copper precursor to 100 parts by weight of the copper nanoparticles. When the copper precursor is less than 10 parts by weight based on 100 parts by weight of the copper nanoparticles There may be a problem that the adhesion is deteriorated due to the lack of copper ions and the formation of oxane bond (oxane bond) becomes difficult. On the other hand, when the amount of the copper precursor is more than 40 parts by weight, the porous structure is formed after the sintering due to the characteristics of the precursor, resulting in a problem that the electrical conductivity is lowered.

According to an embodiment of the present invention, the copper nanoparticles preferably have an average diameter of 5 to 100 nm. When the average diameter of the copper nanoparticles is less than the lower limit, it is difficult to manufacture and it is difficult to expect good conductivity. If the average diameter exceeds the upper limit, the energy required for the bonding is increased and damage to the flexible substrate may occur. So that the resistance can be increased.

The copper precursors are CuCl2, Cu (acac) ₂, Cu (hfac) ₂, Cu (tfac) ₂, Cu (dpm) Cu (nona-F) ₂, can be at least one selected from the group consisting of Cu (acen) ₂, Cu ( NO 3) 2 and H ₂ 0 or CuSO ₄ and H ₂ 0.

The adhesion promoter contained in the copper nano ink improves the adhesion between the substrate activated in the step (I) and the copper nano ink. Examples of the adhesion promoter include an acrylic resin, a chlorinated olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic acid resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, an epoxy resin, an epoxy silane, a monosilane, a trimethoxysilane and a polyimide And a resin.

At this time, the adhesion promoter contained in the copper nano ink preferably contains 1 to 15 parts by weight based on 100 parts by weight of the solvent of the copper nano ink. When the adhesion promoter is less than 1 part by weight, adhesion between the substrate and the copper nano ink Can not be formed sufficiently to improve the adhesion of the copper nano ink. If the amount exceeds 15 parts by weight, the copper nano ink may be deteriorated in conductivity. More preferably, the adhesive strength between the substrate and the copper nano ink is 3 to 10 parts by weight, which is the most excellent.

3, even if the surface of the substrate is activated by plasma or ozone treatment in the step I), if the adhesion promoter is not contained in the copper nano ink, the copper nano ink is exposed on the surface of the substrate (Oxane bond), which is a covalent bond with the hydroxyl group, can not be formed. As a result, the adhesive strength is weakened to have an adhesive strength of 3B or less of 0B to 5B according to ASTM D 3359-97, When the adhesion promoter is contained in the copper nano ink, the adhesion strength is 4B or more.

Next, (III) the copper nano ink is patterned on the surface-treated substrate. At this time, the patterning of the copper nano ink may be performed by a method such as screen printing, inkjet printing, gravuring, bar coater, spraying or the like Can be coated.

Next, the patterned copper nano ink is dried at 70-150 캜. If the patterned copper nano ink is dried at a temperature lower than 70 ° C, the ink may not dry up to the inside of the ink, so that the solvent may escape during sintering, resulting in separation of the substrate and the ink. The solvent of the nano ink may be boiled during drying or the polymer substrate may be damaged.

The copper nano ink patterned on the substrate is preferably dried using a near infrared ray (IR) lamp or an oven. If a xenon lamp or a far ultraviolet lamp is used, sintering is not performed but drying is not performed properly , There is a problem that the copper nano ink is not seated properly on the transparent substrate, and the interface bonding between the copper nano ink is not properly performed, so that a large number of pores are generated in the patterned copper nano ink, which may increase the resistance.

In the present invention, it is preferable to perform photo-sintering in at least two stages using a Xenon lamp or a Xenon lamp and deep UV after the drying. If light sintering is performed in only one step, And patterned copper ink may be produced by bending to weaken the adhesion with the substrate or may cause deformation of the substrate as shown in Fig. 8, and a large number of voids may be formed between the copper particles contained in the copper ink or the copper particles / copper precursor And the sheet resistance is increased. Accordingly, in order to solve such a problem, the present invention performs photo-sintering through multiple steps to prevent deformation of the substrate after sintering or bending of the patterned copper ink.

That is, the present invention controls the light source irradiated from the XENON lamp and the deep UV lamp to multi-photo-sinter the patterned copper nano ink. In this case, the composite light sintering apparatus shown in FIG. Can be used. However, in the case of far ultraviolet rays, it is preferable that the ultraviolet rays are irradiated not simultaneously with the xenon lamp but simultaneously with the xenon lamp, because it acts as an accelerator for improving the reaction of the polymer upon photo-sintering. Although it may be possible to sinter using only the deep ultraviolet ray, since the wavelength band where the resonance phenomenon occurs in the copper nanoparticles is in the visible light band, it is more efficient to use the xenon lamp to sinter it.

Specifically, as described above, the light sintering step is preferably performed in at least two stages. First, the above-mentioned drying is followed by the first photo-sintering by irradiating a Xenon lamp, and then the photo-sintered copper nano ink is irradiated with a deep ultraviolet (UV) lamp and a xenon lamp, Sintered.

When the light energy in the entire wavelength region or the light energy in any one wavelength region is sintered in a very short time, complete sintering is possible. However, when the substrate is deformed or the patterned copper nano- Resulting in a problem of warpage, so that the performance such as adhesion with a substrate, durability and reliability is deteriorated. Therefore, the light sintering step is preferably carried out under the conditions provided in the present invention.

Specifically, the first light sintering step may be performed with a pulse width of 0.5 to 2.0 ms, a pulse gap of 20 to 30 ms, a pulse number of 15 to 30, and a light intensity of 5 to 15 J / cm 2 Preferably a pulse width of 1 to 1.5 ms, a pulse number of 20 to 30 times, a pulse gap of 20 to 30 ms and a light intensity of 8 to 10 J / have.

In the second light sintering step, the pulse width of the xenon lamp is 0.1 to 5 ms, the pulse number is once, the intensity of the light is 5 to 10 J / cm 2, (UV) lamp may be irradiated with 0 to 100 mW / cm < 2 > for 0 to 300 seconds. Preferably, the pulse width is 3 to 5 ms, the number of pulses is 1, Lt; 2 >, and the far ultraviolet lamp may be 45 to 100 mW / cm < 2 >.

It is possible to prevent the phenomenon that the substrate and the copper nano ink are shrunk and warped during the sintering process and the copper nano particles or the copper nano particles contained in the copper nano ink and the copper The resistance is significantly lowered because they are tightly bonded without forming pores between the precursors. In other words, when the first and second light sintering conditions according to the present invention are not satisfied, the patterned copper nano ink is bent at least four times as compared with the patterned copper nano ink according to the present invention, .

Specifically, as shown in Fig. 2A, the substrate or the patterned copper nano ink may be deflected while being shrunk by light sintering. This is a problem caused by attempting to sinter the copper nano ink within a short time by using only simple light sintering. Even if the shrinkage of the substrate is weakened due to preheating, since the conventional copper nano ink has weak adhesion with the substrate, I could not sufficiently prevent it.

However, in the present invention, in order to recognize and overcome the above-described problems, the present invention provides a method of manufacturing a copper soda-lime ink, comprising the steps of: treating a substrate with a plasma; adding an adhesion promoter to copper nano ink; The adhesion of the copper nano particles to the substrate is improved while the shrinkage of the copper nano ink patterned on the substrate is suppressed and the adhesion to the substrate is improved to solve problems such as warping and sag resistance after sintering (Fig. 2B).

According to another aspect of the present invention, the copper nanoink includes 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of a solvent, 50 to 160 parts by weight of a copper nanoparticle or a mixture of copper nanoparticles and a precursor, And 3 to 10 parts by weight of a polymeric binder resin, wherein the adhesion promoter is selected from the group consisting of an acrylic resin, a chlorinated olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, Wherein the copper nano ink is one selected from the group consisting of epoxy silane, monosilane, trimethoxysilane and polyimide resin, and the copper nano ink is patterned through multiple light sintering .

Specifically, the copper nano ink is produced by the multi-light sintering method of the copper nano ink of the present invention described above.

The patterned copper nano ink has a very low resistance of 0.01 to 0.09 Ohm / sq, and it can be confirmed that the electrical conductivity is significantly lower than that of the conventional inks.

Which comprises 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of solvent and 50 to 160 parts by weight of a copper nanoparticle or a mixture of copper nanoparticles and a precursor; And 3 to 10 parts by weight of a polymeric binder resin is sintered through multi-photo-sintering so that the copper nanoparticles or copper nanoparticles contained in the copper nano ink and the copper precursors are sintered So that the resistance is remarkably low. In addition, since the adhesion between the substrate and the copper nano ink is improved, the increase in the interfacial resistance hardly occurs.

In addition, the patterned copper nano ink having the above-described structure is remarkably excellent in durability and reliability against bending to such an extent that the rate of change of resistance is hardly confirmed in repeated outward bending test.

The polymeric binder resin contained in the copper nano ink improves the dispersibility of the ink during the production of the copper nano ink and functions as a reducing agent to remove the oxide film of the copper nanoparticles upon sintering to lower the resistance after sintering. As a result, it is possible to provide a patterned copper electrode pattern with improved electrical conductivity.

The polymeric binder resin contained in the copper nano ink is preferably contained in an amount of 3 to 10 parts by weight based on the total weight of the copper nanoink. When the content of the polymeric binder resin is less than the lower limit of 3 parts by weight, Adhesion between the nano ink and the substrate may be eliminated. If the upper limit is more than 10 parts by weight, it may be difficult to lower the interface resistance at the interface between the copper nanoparticles or the copper nanoparticles and the precursor.

The polymeric binder resin may be, for example, selected from the group consisting of hydroxypropylmethylcellulose (HPMC), polyurethane dispersion (PUD), polyurethane diol, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polymethyl Methacrylate, dextran, or mixtures thereof.

For ease of use of the copper nano ink, a solvent may be included. The solvent may be, for example, 2-butoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol butyl ether, cyclohexanone, cyclohexanol, 2- ethoxyethyl acetate, ethylene Glycol diacetate, terpineol, isobutyl alcohol, and a mixed solution thereof.

The copper nanoparticles and the copper precursor may be mixed in a ratio of 10 to 40 parts by weight of the copper precursor to 100 parts by weight of the copper nanoparticles. When the copper precursor is less than 10 parts by weight based on 100 parts by weight of the copper nanoparticles , It is difficult to form an oxane bond, which is a reaction for improving the adhesion, due to the lack of copper ions. On the other hand, when the amount of the copper precursor is more than 40 parts by weight, the porous structure having a lot of pores after sintering is formed due to the characteristics of the precursor.

According to an embodiment of the present invention, the copper nanoparticles preferably have an average diameter of 5 to 100 nm. When the average diameter of the copper nanoparticles is less than the lower limit, it is difficult to manufacture and it is difficult to expect good conductivity. If the average diameter exceeds the upper limit, the energy required for the bonding is increased and damage to the flexible substrate may occur. So that the resistance can be increased.

The copper precursors are CuCl2, Cu (acac) ₂, Cu (hfac) ₂, Cu (tfac) ₂, Cu (dpm) Cu (nona-F) ₂, can be at least one selected from the group consisting of Cu (acen) ₂, Cu ( NO 3) 2 and H ₂ 0 or CuSO ₄ and H ₂ 0.

The adhesion promoter contained in the copper nano ink improves the adhesion between the substrate and the copper nano ink. Examples of the adhesion promoter include an acrylic resin, a chlorinated olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic acid resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, an epoxy resin, an epoxy silane, a monosilane, a trimethoxysilane and a polyimide A resin, and a resin.

At this time, the adhesion promoter contained in the copper nano ink preferably contains 1 to 15 parts by weight based on 100 parts by weight of the solvent of the copper nano ink. When the adhesion promoter is less than 1 part by weight, adhesion between the substrate and the copper nano ink Can not be formed sufficiently to improve the adhesion of the copper nano ink. If the amount exceeds 15 parts by weight, the copper nano ink may be deteriorated in conductivity. More preferably, the adhesive strength between the substrate and the copper nano ink is 3 to 10 parts by weight, which is the most excellent.

If the adhesion promoter is not contained in the copper nano ink, the copper nano ink can not form a large attractive force such as an oxane bond, which is a covalent bond with the hydroxyl group exposed on the surface of the substrate, And has an adhesive strength of 3B or less in 0B to 5B according to ASTM D 3359-97, but has an adhesive strength of 4B or more when an adhesion promoter is contained in the copper nano ink.

When the light energy in the entire wavelength region or the light energy in any one wavelength region is sintered in a very short time, complete sintering is possible. However, when the substrate is deformed or the patterned copper nano- Resulting in a problem of warpage, so that the performance such as adhesion with a substrate, durability and reliability is deteriorated. Therefore, the light sintering step is preferably carried out under the conditions provided in the present invention.

Specifically, the first light sintering step may be performed with a pulse width of 0.5 to 2.0 ms, a pulse gap of 20 to 30 ms, a pulse number of 15 to 30, and a light intensity of 5 to 15 J / cm 2 Preferably a pulse width of 1 to 1.5 ms, a pulse number of 20 to 30 times, a pulse gap of 20 to 30 ms and a light intensity of 8 to 10 J / have.

In the second light sintering step, the pulse width of the xenon lamp is 0.1 to 5 ms, the pulse number is once, the intensity of the light is 5 to 10 J / cm 2, (UV) lamp may be irradiated with 0 to 100 mW / cm < 2 > for 0 to 300 seconds. Preferably, the pulse width is 3 to 5 ms, the number of pulses is 1, Lt; 2 >, and the far ultraviolet lamp may be 45 to 100 mW / cm < 2 >.

It is possible to prevent the phenomenon that the substrate and the copper nano ink are shrunk and warped during the sintering process and the copper nano particles or the copper nano particles contained in the copper nano ink and the copper The resistance is significantly lowered because they are tightly bonded without forming pores between the precursors. In other words, when the first and second light sintering conditions according to the present invention are not satisfied, the patterned copper nano ink is bent at least four times as compared with the patterned copper nano ink according to the present invention, .

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  One.

1) Manufacture of copper nano ink.

0.8 g of polyvinylpyrrolidone (PVP; MW 40,000, Sigma Aldrich Co, Ltd.) and 9.5 g of diethylene glycol (99%, Sigma Aldrich Co. Ltd) were mixed and dispersed for 2 hours using a sonicator to mix Solution. Copper dispersion was prepared by adding 5.0 g of copper nanoparticles having a diameter of 20 to 50 nm (Quantum Spehere Inc Co. Ltd) and 0.3 g of triethoxysilane. To 1 g of the copper nano ink prepared by removing the copper agglomerate clinging to the dispersion with a filter (pore size: 0.45 탆), 3 ml of a silane coupling agent (KBE-603, Shin-Etsu silicones) 1 ml of Lactone (Wako Pure Chemical Ind. Ltd.), 1 ml of 2-ethoxyethanol (Wako Pure Chemical Ind. Ltd) was added to adjust the surface tension, and the mixture was dispersed using a mixed deaerator and a 3-roll mill Copper nano ink was prepared.

2) Manufacture of copper patterns

The copper nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried at 100 DEG C for 30 minutes using an oven.

Then, copper nano ink uniformly coated on the PI substrate was sintered through multi-stage light sintering. First, in the first light sintering step, the first light sintering step is performed at a pulse width of 1 ms, at a pulse number of 20 times, at a pulse interval of 30 ms, and at a light intensity of 9 J / Water, 7 J / cm2 light intensity.

Example  2.

Copper nano ink prepared according to Example 1-1) was used. The copper nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried at 100 ° C for 30 minutes using an oven.

In the first light sintering step, the light sintering step is performed under the conditions of a pulse width of 1 ms, a pulse number of 20, a pulse interval of 30 ms, and a light intensity of 10 J / The second photo-sintering step was performed under conditions of 5 ms pulse width, one pulse number, and intensity of 6 J / cm 2 light.

Example  3.

Copper nano ink prepared according to Example 1-1) was used. The copper nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried at 100 ° C for 30 minutes using an oven.

Then, copper nano ink, which was uniformly coated on the PI substrate and dried, was sintered through Deep UV, which is a multistage optical element. First, in the first light sintering step, the first light sintering step is performed under the condition of a pulse width of 1 msdml, a pulse number of 30 times, a pulse interval of 30 ms, and a light intensity of 10 J / (Deep UV) of 60 mW / cm < 2 > under the light intensity condition of 5 J / cm < 2 >.

Example  4.

Copper nano ink prepared according to Example 1-1) was used. The copper nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried at 100 ° C for 30 minutes using an oven.

Then, copper nano ink, which was uniformly coated on the PI substrate and dried, was sintered through Deep UV, which is a multistage optical element. First, in the first light sintering step, the pulse width of 1 ms, the pulse number of 30 pulses, the pulse interval of 20 ms, and the light intensity of 8 J / cm 2 are performed. In the second light sintering step, (Deep UV) of 45 mW / cm < 2 > under the light intensity condition of 6 J / cm < 2 >

Example  5.

1) Copper hybrid  Manufacture of nano ink

0.8 g of polyvinylpyrrolidone (PVP; MW 55,000, Sigma Aldrich Co, Ltd.), 4.5 g of diethylene glycol (99%, Sigma Aldrich Co. Ltd) and 4.5 g of 2-ethoxyethanol were mixed and sonicator And dispersed for 2 hours to prepare a mixed solution. To this was added 0.1 g of silane, 11.0 g of copper nanoparticles 20-50 nm in diameter (Quantum Spehere Inc Co. Ltd) and 3 g of copper nitrate precursor to prepare a copper hybrid dispersion. To 1 g of the copper hybrid nano ink prepared by removing the copper agglomerate clinging to the dispersion with a filter (pore size: 0.45 탆), 2 ml of a silane coupling agent (KBE-603, Shin-Etsu silicones) 1 ml of butyrolactone (Wako Pure Chemical Ind. Ltd.) was added and dispersed using a mixed deaerator and a 3-roll mill to prepare a copper hybrid nano ink.

2) Copper hybrid  Manufacture of patterns

The copper hybrid nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried using an oven at 100 ° C. Then, copper hybrid nano ink uniformly coated on the PI substrate was sintered through multi-stage light sintering. In the first light sintering step, the first light sintering step is performed under the conditions of a pulse width of 1 ms, a pulse number of 30, a pulse interval of 30 ms, and a light intensity of 8 J / cm 2, Water, 9 J / cm2 light intensity.

Example  6.

Copper hybrid nano ink prepared in the same manner as in Example 5-1) was prepared except that 0.3 g of silane was added.

The copper hybrid nano ink was uniformly printed on a substrate made of polyethylene polyimide (PI) using a screen printer, and then dried using an oven at 100 ° C for 30 minutes.

Then, the dried copper nano-ink was uniformly coated on the PET substrate and then sintered through a deep ultraviolet ray (Deep UV) in a multi-stage. First, in the first light sintering step, a pulse width of 1 ms, A pulse interval of 30 ms and a light intensity of 8 J / cm 2, and the second light sintering step is performed at a pulse width of 5 ms, a pulse number of 1 pulse, and a light intensity of 8 J / (Deep UV) at the same time.

Example  7.

Copper hybrid nano ink prepared in the same manner as in Example 5-1) was prepared except that 0.3 g of silane and 0.3 g of epoxy were added.

The copper hybrid nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried at 100 ° C for 30 minutes using an oven. Thereafter, the dried copper hybrid nano ink uniformly coated on the PI substrate was sintered through multi-stage light sintering. In the first light sintering step, a pulse width of 1.5 ms, a pulse number of 20 times, a pulse interval of 30 ms, and a light intensity of 10 J / (Deep UV) of 70 mM / cm < 2 > under the condition of 10 J / cm < 2 >

Comparative Example  One.

1) Copper hybrid  Manufacture of nano ink

0.9 g of polyvinylpyrrolidone (PVP; MW 40,000, Sigma Aldrich Co, Ltd.) was mixed with 3.6 g of diethylene glycol (99%, Sigma Aldrich Co. Ltd) and 3.6 g of 2-ethoxyethanol, And dispersed for 2 hours to prepare a mixed solution. To this was added 0.1 g of silane, 12.0 g of copper nanoparticles 20-50 nm in diameter (Quantum Spehere Inc Co. Ltd) and 3 g of copper nitrate precursor to prepare a copper hybrid dispersion. To 1 g of the copper hybrid nano ink prepared by removing the copper agglomerate clinging to the dispersion with a filter (pore size: 0.45 탆), 2 ml of a silane coupling agent (KBE-603, Shin-Etsu silicones) 1 ml of butyrolactone (Wako Pure Chemical Ind. Ltd.) was added and dispersed using a mixed deaerator and a 3-roll mill to prepare a copper hybrid nano ink.

2) Copper hybrid  Manufacture of patterns

The copper hybrid nano ink was uniformly printed on a polyimide (PI) substrate with a screen printer, and then dried in an oven at 100 DEG C for 30 minutes. Then, copper hybrid nano ink uniformly coated on the PI substrate was sintered through multi-stage light sintering. First, in the first light sintering step, the first light sintering step is performed under the condition of a pulse width of 1 ms, 35 pulses, 30 ms pulse interval, and 17 J / cm 2, (Deep UV) of 130 MW / cm < 2 > under a light intensity of 14 J / cm < 2 >

Comparative Example  2.

A copper hybrid nano ink prepared according to Comparative Example 1 was used. The copper hybrid nano ink was uniformly printed on a polyimide (PI) substrate using a screen printer, and then dried in an oven at 100 ° C for 30 minutes.

Thereafter, the dried copper hybrid nano ink uniformly coated on the PI substrate was sintered through multi-stage light sintering. First, in the first light sintering step, a pulse width of 1 ms, a pulse number of 10 pulses, a pulse interval of 30 ms, and a light intensity of 3 J / cm 2 are performed. In the second light sintering step, (Deep UV) of 50 mW / cm < 2 > under a light intensity condition of 4 J / cm < 2 >

Comparative Example  3.

A copper hybrid nano ink prepared according to Comparative Example 1 was used. The copper hybrid nano ink was uniformly printed on a substrate made of polyethylene terephthalate (PET) using a screen printer, and then dried in an oven at 100 ° C for 30 minutes.

Thereafter, the copper hybrid nano ink, which was uniformly coated on the PET substrate and dried, was sintered through multistage light sintering. First, in the first light sintering step, a pulse width of 6 ms, a pulse number of one pulse, a pulse interval of 30 ms, and a light intensity of 13 J / cm 2 are performed. In the second light sintering step, (Deep UV) of 120 mW / cm < 2 > under a light intensity condition of 13 J / cm < 2 >

Comparative Example  4.

A copper hybrid nano ink prepared according to Comparative Example 1 was used. The copper hybrid nano ink was uniformly printed on a substrate made of polyethylene terephthalate (PET) using a screen printer, and then dried in an oven at 100 ° C for 30 minutes.

Thereafter, the copper hybrid nano ink, which was uniformly coated on the PET substrate and dried, was sintered through multistage light sintering. First, in the first light sintering step, a pulse width of 1 ms, a pulse number of 10 pulses, a pulse interval of 30 ms, and a light intensity of 3 J / cm 2 are performed. In the second light sintering step, (Deep UV) of 50 mW / cm < 2 > under a light intensity condition of 4 J / cm < 2 >

Comparative Example  5.

Copper hybrid nano ink prepared in the same manner as in Comparative Example 1 was used except that silane was not included. The copper hybrid nano ink was uniformly printed on a substrate made of polyethylene terephthalate (PET) using a screen printer, and then dried in an oven at 100 ° C for 30 minutes.

Then, the dried copper hybrid nano ink was uniformly coated on the PET substrate and sintered through a single step of light sintering. The light sintering step was performed under conditions of a pulse width of 1 ms, a pulse number of 10 times, a pulse interval of 30 ms, and a light intensity of 3 J / cm 2.

Comparative Example  6.

Copper hybrid nano ink prepared in the same manner as in Comparative Example 1 was used except that 0.5 g of silane was contained. The copper hybrid nano ink was uniformly printed on a substrate made of polyethylene terephthalate (PET) using a screen printer, and then dried in an oven at 100 ° C for 30 minutes.

Then, the dried copper hybrid nano ink was uniformly coated on the PET substrate and sintered through a single step of light sintering. The light sintering step was performed under conditions of a pulse width of 1 ms, a pulse number of 10 times, a pulse interval of 30 ms, and a light intensity of 3 J / cm 2.

Evaluation example  1. Patterned Copper Nano Ink Sheet resistance  Measure

The sheet resistance of the patterned copper nanoink was measured under various light sintering conditions.

5 is a graph showing the sheet resistance of the patterned copper nano ink prepared according to Examples 1 to 7 of the present invention. At this time, the copper nano inks of Examples 1 to 7 are listed in order from 1 to 7 shown in the graph.

As a result, it can be confirmed that the copper nano ink patterned under the light sintering condition according to the present invention has a significantly lower sheet resistance of 0.01 to 0.09 Ohm / sq.

Evaluation example  2. Scanning Electron Microscopy Analysis of Patterned Copper Nano Ink

FIG. 6 is an electron micrograph of a patterned copper nano ink prepared from Example 3 of the present invention before photo-sintering, after the first photo-sintering step and after the second photo-sintering step.

As a result, it was possible to observe printed copper nanoparticles by polymer coating before photo-sintering. Thereafter, when only the first-stage photo-sintering is performed, sintering is performed, but it can be seen that many pores are formed between the copper nanoparticles.

On the other hand, in the case of performing both of the second-stage photo-sintering, the sintering is well performed, the copper nanoparticles are completely bonded to each other, the pores are small and the density is high, It can be understood that the electric conductivity is significantly superior to that in the case of performing under different light sintering conditions. In addition, due to this complete sintering, it is expected that the patterned copper nano ink will increase the bending property and increase the reliability in fatigue life.

Evaluation example  3. Analysis of adhesive force characteristics of patterned copper nano ink

The adhesion properties of the patterned copper nano ink with addition of silane and epoxy were tested. Specifically, the patterned copper nanoinks prepared in Examples 5, 6, and 7 were placed on a cut pattern of a 1-inch wide translucent pressure-sensitive Permacel 99 tape and rubbed with a rubber eraser to adhere closely. Subsequently, the tape was quickly pulled from the substrate, and the most favorable one according to ASTM D 3359-97 was rated as 5B, and the worst one as OB, and the adhesive strength was graded.

The adhesiveness was tested according to the same procedure as the above-described adhesion test, and the results are shown in Fig.

FIG. 7 is a photograph showing the adhesive force characteristics of the patterned copper nano ink prepared in Example 5, Example 6 and Example 7 of the present invention. As shown in FIG. 7, when silane or epoxy is added, It can be seen that the adhesion to the patterned copper nano ink is remarkably improved. Particularly, it can be confirmed that when the silane is 3 wt% or the silane and epoxy are simultaneously added at 3 wt%, 5B is remarkably improved.

Evaluation example  4. Characteristic analysis of patterned copper nano ink

In order to investigate the effect of light sintering conditions on the warping characteristics of the substrate or patterned copper nano ink, we measured the degree of warping under various light sintering conditions.

Specifically, one end of the substrate is fixed to the bottom with a tape, and copper nano ink is printed on the substrate, followed by drying and photo-sintering under various conditions. At this time, the substrate or the copper nano ink is shrunk and warped. That is, after the light sintering process was finished, the other end corresponding to the end of the substrate was bent from the bottom by bending according to the sintering condition, and the height of the substrate was measured to confirm the degree of warpage.

The bending characteristics were tested according to the same procedure as the above-described bending characteristic test, and the results are shown in Fig.

8 is a photograph showing the warpage characteristics of the patterned copper nano ink prepared from Example 1 of the present invention and Comparative Example 1 and Comparative Example 5. As shown in FIG. 8, the optimum light sintering condition In the case of the patterned copper nano ink performed, only 0.15 mm bend.

However, when the optical sintering condition of the present invention is not met (other condition), it can be confirmed that 0.61 mm is warped, which is four times larger than that of the optimized patterned copper nano ink of the present invention.

In addition, it can be seen that the patterned copper nanoink produced by a single-stage photo-sintering process warped to 1.42 mm in one step, which is more than 9 times as high as that of the optimized patterned copper nanoink of the present invention It is a big figure.

As a result of the above-mentioned results, in the production of the copper nano ink patterned through the multi-photo-sintering, the shrinkage rate of the substrate is remarkably changed when the conditions of each step in the multi-light sintering are changed, The resistance of the ink is greatly increased.

Evaluation example  5. Reliability measurement of patterned copper nano ink

FIG. 9 is a graph showing the resistance change of the patterned copper nano-ink when the patterned copper nano ink prepared in Comparative Examples 5 and 6, which is a single-step light sintering method, is repeatedly subjected to a bending test .

FIG. 10 shows the results of the repeated outward bending tests of the patterned copper nanoinks prepared in Example 1, Example 5, Example 6, and Example 8, which are multistage optical sintering methods, This graph is a graph measuring the resistance change of nano ink.

As a result, the patterned copper nano ink produced by the single-step photo-sintering method showed a high resistance rise rate and low reliability in the repeated lateral bending test. On the other hand, the repetitive lateral bending test of the patterned copper nano ink produced by the light sintering method according to the present invention showed a low resistance increase rate and high reliability.

However, even if the copper nano ink is patterned by the multi-light sintering method, it is confirmed that when the copper nano ink does not contain silane, the resistance increase rate is increased as in Comparative Examples 5 and 6, and the reliability is remarkably lowered.

Evaluation example  6. In Comparative Example  Of the patterned copper nanoink Sheet resistance  Measure

11 is a graph showing the sheet resistance of the patterned copper nano ink prepared in Comparative Examples 1 to 4 of the present invention.

As a result, it can be seen that the resistance increases from 0.2 Ohm / sq to 1.2 Ohm / sq when the light sintering condition of the present invention is deviated. Which is 2 to 10 times higher than the resistance of the patterned copper nano ink according to the present invention.

Evaluation example  7. In Comparative Example  Of Adhesive Properties of Patterned Copper Nano Ink

Fig. 12 is a photograph showing the adhesive force characteristics of the patterned copper nano ink prepared in Comparative Examples 1 to 4 of the present invention.

As a result, it was confirmed that the bonding strength with the substrate was significantly lowered by OB even when an adhesion promoter such as silane or epoxy was added when the light sintering condition of the present invention was exceeded.

That is, it can be confirmed that the patterning of the copper nano ink under the light sintering condition of the present invention is significantly superior to the patterning through general light sintering, such as sheet resistance, electrical conductivity, adhesive strength to the substrate and reliability.

Claims (10)

I) treating the substrate surface with oxygen plasma or ozone gas;
II) 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of a solvent; and 50 to 160 parts by weight of a copper nanoparticle or a mixture of copper nanoparticles and a precursor; And 3 to 10 parts by weight of a polymeric binder resin;
III) patterning the copper nano ink on the surface-treated substrate;
Drying the patterned copper nano ink at 70 to 150 캜;
V) a step of irradiating a Xenon lamp after the drying to perform first photo-sintering; And
(VI) a second photo-sintering step of irradiating the photo-sintered copper nano ink with a deep ultraviolet (UV) lamp and a xenon lamp. The method according to claim 1,
The solvent may be selected from the group consisting of 2-butoxy ethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol butyl ether, cyclohexanone, cyclohexanol, 2-ethoxyethyl acetate, ethylene glycol diacetate, Wherein the solvent is any one selected from the group consisting of terpineol, isobutyl alcohol, and a mixture thereof. The method according to claim 1,
Wherein the mixture of the copper nanoparticles and the copper precursor is mixed at a ratio of 10 to 40 parts by weight of the copper precursor to 100 parts by weight of the copper nanoparticles. The method according to claim 1,
The polymeric binder resin may be selected from the group consisting of hydroxypropylmethylcellulose (HPMC), polyurethane dispersions (PUD), polyurethane diols, polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, Wherein the copper-based ink is one selected from the group consisting of polyvinyl chloride, acrylate, acrylate, acrylate, acrylate, acrylate, acrylate, acrylate, The method according to claim 1,
The average diameter of the copper nanoparticles is 5 to 100 nm,
The copper precursors are CuCl2, Cu (acac) ₂, Cu (hfac) ₂, Cu (tfac) ₂, Cu (dpm) Cu (nona-F) ₂, Cu (acen) ₂, Cu (NO 3) 2 and H ₂ 0 or CuSO ₄ and a multi-light of the copper nano-ink, characterized in that at least one selected from the group consisting of H ₂ 0 Sintering method. The method according to claim 1,
Wherein the adhesion promoter is selected from the group consisting of an acrylic resin, an olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic acid resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, an epoxy resin, an epoxy silane, a monosilane, a trimethoxysilane and a polyimide resin Wherein the copper nanopowder is one selected from the group consisting of copper nanoparticles, copper nanoparticles, and copper nanoparticles. The method according to claim 1,
Characterized in that the patterning step is performed by screen printing, inkjet printing, gravuring, bar coater or spraying. The multi-photo-sintering of copper nanoinks Way. The method according to claim 1,
Wherein the first light sintering step is 0.5 to 2.0 ms, the pulse gap is 20 to 30 ms, the number of pulses is 15 to 30, and the light intensity is 5 to 15 J / cm 2. ≪ / RTI > The method according to claim 1,
In the second light sintering step, the pulse width of the xenon lamp is 0.1 to 5 ms, the pulse number is 1 to 3 times, the intensity of the light is 5 to 10 J /
Wherein the power of the far ultraviolet (UV) lamp is irradiated at 0 to 100 mW / cm < 2 > for 0 to 300 seconds. A multi-photo-sintered patterned copper nanoink according to claim 1,
Wherein the copper nano ink comprises 1 to 15 parts by weight of an adhesion promoter based on 100 parts by weight of the solvent and 50 to 160 parts by weight of a copper nanoparticle or a mixture of copper nanoparticles and a precursor; And 3 to 10 parts by weight of a polymeric binder resin,
Wherein the adhesion promoter is selected from the group consisting of an acrylic resin, an olefin resin, a vinyl chloride vinyl acetate copolymer resin, a maleic acid resin, a chlorinated rubber resin, a polysiloxane, a styrene resin, an epoxy resin, an epoxy silane, a monosilane, a trimethoxysilane and a polyimide resin Wherein the copper nano-ink is at least one selected from the group consisting of copper, niobium, and tin.

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