KR20150088186A - Preparation method of Electrode and Separation type Electrode paste composition for electrical materials - Google Patents

Abstract

The present invention relates to a method for manufacturing an electrode and an electrode paste composition for a peelable electronic material. The method for manufacturing an electrode comprises: a step (a) of printing an electrode pattern on a substrate by using an electrode paste composition; a step (b) of forming a plastic body of the electrode pattern by burning the substrate on which the electrode paste composition is printed; and a step (c) of stripping and transiting the plastic body of the electrode pattern from the substrate. The present invention has effects of manufacturing an electrode without the conventional etching and plating processes, and being environmentally friendly, and implementing low resistance required for an electrode of an electronic material.

Description

[0001] The present invention relates to a method for manufacturing an electrode, and an electrode paste composition for an exfoliative electronic material.

The present invention relates to a method for producing an electrode and an electrode paste composition for a peelable electronic material.

Some of the low-temperature electrode manufacturing processes used in electronic materials are mainly used in two ways.

First, there is a method in which a Cu foil or an Al foil is laminated on a PI film or a PET film, and an unnecessary portion other than a desired circuit pattern is etched to realize an electrode pattern. That is, in the conventional method, there is a method in which etching after foil laminating is essentially used at the time of pattern formation.

Secondly, there is a method of printing and drying on a substrate using Ag paste and Cu paste, and then forming a final electrode including an electrode pattern through a plating process.

However, the first method requires a complex process such as development, etching, peeling, washing and the like, and since a considerable material such as a photosensitive film or an etching solution is used as a process material, there is a problem of polluting the environment while raising the price of the product. In addition, since the second method can not reach the required resistance only by drying after the printing of the metal paste, a copper plating process must be further performed on the electrode, and the plating solution is extremely harmful to the environment.

In addition, a conductive polymer is used as an electrode-forming material. In the case of a coating film using the conductive polymer, however, there is a problem in that reliability is lowered due to an increase in sheet resistance depending on a period for use as an electrode-forming material.

It is an object of the present invention to simplify a manufacturing process of an electrode for a conventional electronic material and to develop an electrode material and a process which can be replaced with a reduction in manufacturing cost and an environmentally friendly process.

Accordingly, it is an object of the present invention to provide a method of manufacturing an electrode which is capable of realizing a necessary resistance even when a conventional etching and plating process is not performed, and is not harmful to the environment.

Another object of the present invention is to provide a method of manufacturing an electrode which is simple in the manufacturing process owing to the omission of the etching and plating process and thus has a cost and a facility saving effect as well as an excellent reliability.

Still another object of the present invention is to provide an electrode paste composition for a peelable electronic material used in the production of the electrode.

(A) printing an electrode pattern on a substrate using an electrode paste composition;

(b) firing a substrate on which the electrode paste composition is printed to form a fired body of the electrode pattern; And

(c) separating and transferring the sintered body of the electrode pattern from the substrate;

The present invention also provides a method of manufacturing an electrode including the electrode.

Wherein the substrate is a ceramic substrate having a surface roughness Ra of 0.01 to 0.5. Further, the substrate is a ceramic substrate including alumina or aluminum nitride.

In the step of peeling and transferring the fired body of the electrode pattern, the fired body of the electrode pattern can be peeled and transferred from the substrate by using an adhesive film, an adhesive tape or a double-sided tape.

The calcination may be performed at a temperature of 400 to 900 DEG C for 2 to 600 minutes.

The electrode paste composition may include a conductive metal having an average particle diameter of 20 to 900 nm, a binder, an organic solvent, and a dispersant. The conductive metal may be at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles.

The present invention also relates to a conductive paste composition comprising 50 to 90% by weight of a conductive metal having an average particle diameter of 20 to 900 nm, 1 to 20% by weight of a binder, 1 to 30% by weight of an organic solvent and 0.1 to 10% The present invention provides an electrode paste composition for a peelable electronic material.

The electrode paste composition may further include at least one selected from the group consisting of spherical silver powder having an average particle size of 1 to 5 탆, gold powder, Ag coated Cu powder, Cu powder, Al, and ZnO powder.

The binder may be selected from the group consisting of acrylic resin, epoxy resin, polyester resin, polyurethane resin, amino resin, phenol resin, vinyl resin, ethyl cellulose, hydroxypropylethylcellulose, Polyvinyl resins, and polyvinyl resins.

The organic solvent may be at least one selected from the group consisting of terpineol, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol, texanol, butyl carbitol acetate, dimethyl formamide, acetylacetone, Propyl ketone, and ethyl lactate.

In the present invention, the conductive metal may be at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles.

The present invention also provides an electrode for a flexible circuit board manufactured by the above-described method. At this time, the electrode for the flexible circuit board may include an NFC antenna, an antenna for a WPC (wireless charger), an IOT (object internet), a BLU, a TSP, a digitizer, a camera module, or a banding type electrode.

The present invention can realize a necessary resistance even without etching and plating processes by producing the electrode for the final device through the printing and firing of the conductive electrode paste and the peeling and transferring process of the fired electrode after the firing, It is effective to reduce the cost. Further, since the electrode fired body of the present invention has flexibility, it can be applied to various fields requiring flexible electrode characteristics. In addition, the electrode of the present invention can be applied to manufacture various electrodes applied to a flexible circuit board. In particular, the electrode paste composition of the present invention can be used for an NFC antenna, an antenna for a wireless charger, an IOT (object internet), a BLU, a TSP, a digitizer, a camera module, It is applicable to electrode manufacturing.

Hereinafter, the present invention will be described in detail.

According to an embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) printing an electrode pattern on a substrate using an electrode paste composition; (b) firing a substrate on which the electrode paste composition is printed to form a fired body of the electrode pattern; And (c) separating and transferring the sintered body of the electrode pattern from the substrate.

The electrode paste composition may include a conductive metal having an average particle diameter of 20 to 900 nm, a binder, an organic solvent, and a dispersant. The conductive metal may be at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles. Preferably, the electrode paste composition comprises 50 to 90% by weight of a conductive metal containing spherical Ag, Ag coated Cu, Au, Cu, Al, or ZnO particles having an average particle size of 20 to 900 nm, %, 1 to 30% by weight of an organic solvent and 0.1 to 10% by weight of a dispersant.

The present invention is characterized by using an electrode paste composition for a peelable electronic material having the composition as described above. Therefore, it is possible to manufacture an electrode by a simple process which is not harmful to the environment and exhibits a desired resistance without a separate etching process or a plating process have. Since the electrode thus manufactured has excellent flexibility, it can be applied to various kinds of flexible devices. Also, since the electrode manufactured according to the present invention has peeling property and flexibility, the method of the present invention is a peelable electrode manufacturing process which can be used for a desired electronic material substrate.

In the method of manufacturing an electrode of the present invention, the substrate is characterized by using a ceramic substrate having a surface roughness Ra of 0.01 to 0.5.

More specifically, the ceramic substrate used in the present invention is a substrate that can withstand high temperatures when firing an electrode. However, in a ceramic substrate having no deformation at 1000 占 폚 or more, the peeling characteristics vary depending on the surface roughness, so that it is necessary to manage the roughness characteristics of the substrate. Therefore, in the present invention, it is preferable that the surface roughness of the ceramic substrate has an Ra value of 0.01 to 0.5 in consideration of the optimum peeling property at the time of electrode production. If the Ra value is less than 0.01, a precise surface lapping operation of the ceramic substrate is added. Therefore, there is a problem of an increase in the price, and when the Ra value exceeds 0.5, the roughness of the surface of the ceramic substrate is poor.

Preferable examples of the ceramic substrate exhibiting such a specific roughness value include a ceramic substrate including alumina or aluminum nitride. Conventional commonly used glass can not be peeled off, and a polyimide film (PI film) can not be fired. Therefore, it is possible to manufacture an electrode which can be easily peeled off by applying a ceramic substrate exhibiting a specific roughness value according to the present invention.

Further, in the present invention, an adhesive component can be used when the fired body of the electrode pattern is peeled off. The adhesive component is a medium for separating the fired bodies baked on the ceramic substrate and transferring the fired bodies to another substrate. Therefore, the electrode fired body, preferably the Ag prism body, moves from the ceramic substrate to another electronic material substrate through the adhesive component. Such a pressure-sensitive adhesive component is not limited in its thickness. Preferably, in the step of peeling and transferring the sintered body of the electrode pattern, the sintered body of the electrode pattern can be peeled and transferred from the substrate by using an adhesive film (Stacky film), an adhesive tape or a double-sided tape as the adhesive component . An example of the method of peeling and transferring the fired body of the electrode pattern is that the fired electrode can be easily transferred from the ceramic substrate to another electronic material by simply raising and removing the pressure-sensitive adhesive film on the fired electrode.

Further, according to the present invention, the firing can be performed at a temperature of 400 to 900 DEG C for 2 to 600 minutes. The firing may be carried out in a Box firing furnace or a belt firing furnace.

According to another preferred embodiment of the present invention, it comprises 50 to 90% by weight of a conductive metal having an average particle diameter of 20 to 900 nm, 1 to 20% by weight of a binder, 1 to 30% by weight of an organic solvent and 0.1 to 10% And an electrode paste composition for a peelable electronic material is provided, which is used for the production of the above-mentioned electrode.

The electrode paste composition may further include at least one selected from the group consisting of spherical silver powder having an average particle size of 1 to 5 탆, gold powder, Ag coated Cu powder, Cu powder, Al, and ZnO powder.

Since such an electrode paste composition has a composition excellent in peeling property compared with the conventional one, a peelable electrode can be manufactured by an easy method.

At this time, the present invention can improve the peelability from the substrate by using a nano-sized silver powder as the conductive metal. Namely, since the nano-sized powder has a large shrinkage ratio, it provides a favorable effect for peeling.

Therefore, it is preferable that the conductive metal includes at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles having an average particle diameter of 20 to 900 nm, And may include at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles having an average particle size of 100 to 500 nm. It is most preferable to use spherical Ag or Ag coated Cu particles having an average particle diameter of 100 to 500 nm as the conductive metal.

In addition, the electrode paste composition of the present invention preferably further comprises a mixture of micro-sized metal powders in addition to the nano-sized conductive metal powder. The micro-sized metal powder may be at least one selected from the group consisting of spherical silver powder having a micro size, gold powder, Ag coated Cu powder, Cu powder, Al, and ZnO powder. The micro-sized metal powder may have an average particle diameter of 1 to 5 mu m.

In this case, as a preferable example, it is preferable that the conductive metal of the present invention includes a mixture of a micro-sized metal powder and a nano-sized metal powder. The micro-sized metal powder and the nano-sized metal powder may be mixed in a weight ratio of 1:99 to 99: 1 in the total conductive metal used for the electrode paste composition. At this time, when the conductive metal is mixed with only spherical or plate-shaped Ag powder of micro size as before, the peeling property is deteriorated.

When the content of the conductive metal is less than 50% by weight, there arises a problem that the resistance of the electrode is lowered due to a high debinding rate at the time of firing and the density of the electrode is decreased. When the content exceeds 90% by weight, And there is a problem of price increase.

In the present invention, the binder may be selected from the group consisting of acrylic resin, epoxy resin, polyester resin, polyurethane resin, amino resin, phenol resin, vinyl resin, ethyl cellulose, hydroxypropyl ethyl cellulose, , Monobutyl ether, and polyvinyl resin. The binder may be debinded in the post-firing process of the electrode paste composition. If the content of the binder constituting the electrode paste composition of the present invention is less than 1% by weight, it is difficult to secure the printable rheology property of the paste. If the content exceeds 20% by weight, And there is a problem that the density of the electrode is lowered during debinding.

In addition, the electrode paste composition may further include at least one conductive polymer selected from the group consisting of polyaniline, polypyrrole, polythiophene, and derivatives thereof, if necessary. At this time, the conductive polymer may be used in a form of a solution having a solid content of 0.1 to 5.0 wt%, and may be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the electrode paste composition.

In addition, the organic solvent may be contained in a residual amount relative to the whole composition, but may be preferably used in an amount of 1 to 30% by weight based on the weight of the entire electrode paste composition.

The organic solvent may be at least one selected from the group consisting of terpineol, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol, texanol, butyl carbitol acetate, dimethyl formamide, acetylacetone, Propyl ketone, and ethyl lactate.

In addition, since the dispersing agent can use materials well known in the art, the kind and content range thereof are not particularly limited. Preferably, the dispersing agent is used in an amount of 0.1 to 10% by weight based on the total weight of the electrode paste composition.

The method for producing the electrode paste composition of the present invention is not particularly limited, and is manufactured by mixing the respective components described above. In this case, unlike the electrode material used in the conventional low-temperature type electronic material substrate, the curing process is performed by using a curing agent, and unlike the method of performing the plating process, a low resistance can be realized through only the firing process without the curing agent And thus can be used for manufacturing the electrode as described above.

According to another embodiment of the present invention, there is provided an electrode for a flexible circuit board manufactured by a method according to the above-described method.

That is, the electrode of the present invention can be used for application to a flexible circuit board. Particularly, the electrode of the present invention is applied to a flexible circuit board, and can be used for an NFC antenna, an antenna for a wireless charger, an IOT (Internet), a BLU, a TSP, a digitizer, a camera module, It is preferable to use it for the production of

In this case, the present invention can easily manufacture the peelable electrode without etching and plating processes as in the conventional method, and the electrode can be effectively used for the peelable electronic material because of its excellent performance.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

≪ Comparative Example 1 &

, 80 wt% of a conductive metal (plate-shaped silver powder having an average particle diameter of 1.5 탆), 6 wt% of a binder (polyester), 8 wt% of an organic solvent (propylene glycol monomethyl ether), 5.5 wt% of a curing agent (BI- BYK-111) were mixed to prepare an electrode paste composition.

Then, the electrode paste was printed on the PI film in an electrode pattern, and dried and cured at 120 캜 for 30 minutes to prepare an Ag electrode. Then, copper was plated on the Ag electrode by a conventional method to prepare an electrode. That is, in Comparative Example 1, the paste was printed and dried on a flexible substrate by a general method, and then a plating process was performed using a copper plating solution to prepare an electrode.

≪ Example 1 >

90 weight% of a mixture of a conductive metal (spherical silver powder having an average particle diameter of 200 nm and spherical silver powder having an average particle diameter of 1.3 탆) (weight ratio = 1: 0.7 (weight ratio of all conductive metals) = 39: 61) 4.5% by weight of a binder (hydroxypropylmethylcellulose), 5% by weight of an organic solvent (propylene glycol monomethyl ether) and 0.5% by weight of a dispersant (BYK-108) were mixed to prepare an electrode paste composition.

An alumina substrate having a thickness of 1 mm was prepared, and an electrode paste was printed on the substrate in an electrode pattern. Then, the sintered body was baked in a Box baking furnace at 600 ° C for 30 minutes without a separate curing process. At this time, as shown in Table 2 below, a ceramic substrate having various Ras was used in the production of an electrode (an alumina substrate with a thickness of 1 mm (Ra = 0.01 to 0.5) and aluminum nitride (Ra = 0.2 to 0.5)).

Subsequently, the Ag fired body was peeled and transferred from the substrate using an adhesive film having a thickness of 0.05 mm to prepare an electrode.

≪ Examples 2 to 8 &

An electrode was prepared in the same manner as in Example 1, except that the composition and the content were changed as shown in Table 1 below. However, in Examples 6 to 7, N ₂ gas was injected into the box baking furnace during the high-temperature firing process, and firing was performed in a stable nitrogen atmosphere, thereby preventing the oxidation of Cu.

Example One 2 3 4 5 6 7 8 Conductive metal
(Conductive particles) Silver powder, 1.5 占 퐉 (wt%) 35 10 Silver powder, 1.3 占 퐉 (wt%), 35 55 10 Silver powder, 400 nm (wt%), 55 45 At 200 nm (wt%), 55 35 70 45 55 55 55 Ag coated Cu 35 Cu powder 35 Au powder 35 bookbinder Hydroxypropyl methylcellulose (wt%) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 abandonment
menstruum Propylene glycol monomethyl ether (wt%) 5 5 5 5 5 5 5 5 additive Dispersant (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

≪ Comparative Examples 2 to 3 >

An electrode was prepared in the same manner as in Example 1, except that the composition and content were changed as shown in Table 2 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Conductive metal
(Conductive particles) Silver powder, 1.5 占 퐉 (wt%) 80
(Plate type) 35 Silver powder, 1.3 占 퐉 (wt%), 55 90 Silver powder, 400 nm (wt%), At 200 nm (wt%), Ag coated Cu Cu powder Au powder bookbinder Polyester (wt%) 6 Hydroxypropyl
Methyl cellulose (wt%) 4.5 4.5 abandonment
menstruum Propylene glycol
Monomethyl ether (wt%) 8 5 5 Hardener BI-180 (wt%) 5.5 additive Dispersant (wt%) 0.5 0.5 0.5

<Experimental Example>

Resistances of the electrodes of Examples 1 to 8 and Comparative Examples 1 to 3 were measured by a conventional method, and the results are shown in Table 3.

In Examples 1 to 8 and Comparative Examples 1 to 3 as shown in Table 3 below, various experiments were conducted according to Ra of the substrate (an alumina substrate with a thickness of 1 mm (Ra = 0.01 to 0.5), aluminum nitride (Ra = 0.2 to 0.5)). The results of peeling properties for each substrate were measured in accordance with the following criteria and the results are shown in Table 3.

&Amp; cir &amp;: When the Ag-sintered body was peeled off from a ceramic substrate with a low adhesive film (Stacky Film)

○: When the Ag-sintered body was peeled off from the ceramic substrate with a focusing film (3M 810 Scotch Magic Tape)

DELTA: When the Ag-sintered body was peeled off from the ceramic substrate by a high-adhesion film (3M 610 Scotch Tape)

X: No peeling at all when the Ag fired body was peeled from the ceramic substrate

Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 Line resistance (Ω / 60cm) 0.5 0.6 0.8 0.6 1.0 1.2 1.3 0.4 0.8 1.3 1.3 Plastic Thickness (um) 15 17 18 16 16 15 14 13 15
Dry thickness 20 19 Exfoliation
characteristic Al ₂ O ₃
(96% purity)
Ra value of 0.5 or more X X X X X X X X X X Al ₂ O ₃
(96% purity)
Ra value 0.2 to 0.5 △ △ △ △ △ △ △ △ X X Al ₂ O ₃
(96% purity)
Ra value 0.01 to 0.05 ○ ○ ○ ○ ◎ ○ ○ ◎ △ △ Al ₂ O ₃
(Purity 99.9%)
Ra value 0.2 to 0.5 ○ ○ ○ ○ ○ ○ ○ ○ X X AlN
Ra value 0.2 to 0.5 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ △ △

From the results of Table 3, it can be seen that Examples 1 to 8 of the present invention are low in line resistance, compared to Comparative Examples 1 to 3, and have excellent overall thickness and delamination properties. On the other hand, Comparative Example 1 is required to undergo a curing process and also requires an etching and plating process, and Comparative Examples 2 and 3 do not use nano-sized silver powder.

From these results, it can be seen that the present invention can manufacture electrodes more efficiently than conventional processes. In other words, the present invention can provide an electrode capable of realizing a required resistance even without a separate plating process, thereby preventing environmental harmful factors. Further, since the present invention uses a ceramic substrate having a specific roughness value, it is possible to peel and transfer the electrode by a simple method after the firing process, so that electrodes for various electronic materials capable of realizing a low resistance can be easily provided .

Claims (14)

(a) printing an electrode pattern on a substrate using an electrode paste composition;
(b) firing a substrate on which the electrode paste composition is printed to form a fired body of the electrode pattern; And
(c) separating and transferring the sintered body of the electrode pattern from the substrate;
Wherein the electrode is formed of a metal.
The method according to claim 1,
Wherein the substrate is a ceramic substrate having a surface roughness Ra of 0.01 to 0.5.
3. The method according to claim 1 or 2,
Wherein the substrate is a ceramic substrate comprising alumina or aluminum nitride.
The method according to claim 1,
Wherein in the step of peeling and transferring the fired body of the electrode pattern, the fired body of the electrode pattern is peeled and transferred from the substrate by using an adhesive film, an adhesive tape or a double-sided tape.
The method according to claim 1,
Wherein the firing is performed at a temperature of 400 to 900 DEG C for 2 to 600 minutes.
The method according to claim 1,
Wherein the electrode paste composition comprises a conductive metal having an average particle diameter of 20 to 900 nm, a binder, an organic solvent and a dispersant.
The method according to claim 6,
Wherein the conductive metal is at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles.
1 to 20% by weight of a binder, 1 to 30% by weight of an organic solvent and 0.1 to 10% by weight of a dispersant, wherein the conductive metal has an average particle diameter of 20 to 900 nm, &Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
Electrode paste composition for peelable electronic material.
9. The method of claim 8,
Wherein the electrode paste composition further comprises at least one selected from the group consisting of spherical silver powder having an average particle size of 1 to 5 占 퐉, gold powder, Ag coated Cu powder, Cu powder, Al, and ZnO powder.
9. The method of claim 8,
The binder may be selected from the group consisting of acrylic resin, epoxy resin, polyester resin, polyurethane resin, amino resin, phenol resin, vinyl resin, ethyl cellulose, hydroxypropyl ethyl cellulose, And a polyvinyl resin. The electrode paste composition for a peelable electronic material according to claim 1,
9. The method of claim 8,
The organic solvent may be at least one selected from the group consisting of terpineol, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol, texanol, butyl carbitol acetate, dimethyl formamide, acetylacetone, Wherein the electrode paste composition is at least one selected from the group consisting of propyleneglycol, propyleneglycol, propyleneglycol, propyleneglycol, ethyleneglycol, propyleneglycol, propyleneglycol, propyleneglycol,
9. The method of claim 8,
Wherein the conductive metal is at least one selected from the group consisting of spherical Ag, Ag coated Cu, Au, Cu, Al, and ZnO particles.
An electrode for a flexible circuit board produced by the method according to claim 1.
14. The method of claim 13, wherein the electrode is a flexible circuit board including an NFC antenna, an antenna for a wireless charger, an IOT, a BLU, a TSP, a digitizer, a camera module, Electrode.