KR102457877B1 - Photocurable ceramic complex ink composition and manufacturing method of printed circuit board - Google Patents

Abstract

The present invention is a photocurable ceramic composite ink composition for forming the insulating layer by inkjet 3D printing to form an insulating layer formed under the conductor line of a printed circuit board, SiO ₂ sol 2-45 wt. %; 1-20 wt% of at least one oxide nanoparticle selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ; 50-90 wt% of monomer; 0.1 to 6 wt% of a surface modifier; And it relates to a photocurable ceramic composite ink composition comprising 0.01 to 3 wt% of a photoinitiator, and a method for manufacturing a printed circuit board using the same. According to the present invention, the insulating layer of the printed circuit board can be easily formed using inkjet 3D printing, and the printed circuit board can be easily formed.

Description

Photocurable ceramic complex ink composition and method of manufacturing a printed circuit board using the same

The present invention relates to a photocurable ceramic composite ink composition and a method for manufacturing a printed circuit board using the same, and more particularly, to a photocurable ceramic composite ink composition capable of forming an insulating layer of a printed circuit board using inkjet 3D printing, and It relates to a method of manufacturing a printed circuit board using the same.

3D (3 dimensional) printing technology is a process technology for manufacturing a three-dimensional shape by repeatedly laminating a desired material in a two-dimensional cross section from digital data designed in three dimensions. Design and modification are very free, consume less material than conventional cutting, and unnecessary manufacturing process can be omitted, which greatly reduces manufacturing process cost and time. Various types of 3D printing equipment have been developed according to the lamination method, and the demand for the development of new materials for 3D printing corresponding thereto is also increasing.

Recently, 3D printing technology is actively researching to apply a new material that exhibits excellent physical and chemical performance, such as ceramic, with a polymer, away from the existing polymer-oriented material, and apply it to 3D printing. Until now, the material industry has focused on the development of new materials to meet the high performance demanded by the demand industry. are receiving

Types of 3D printing technology include SLS (Selective laser sintering), FDM (Fused deposition modeling), SLA (Stereo lithography apparatus), Ink-jet, Binder jet, etc., depending on the layering method and available materials. can be distinguished as

Among them, the inkjet printing method is a technique for discharging fine ink droplets from a head and patterning them at a desired location. Inkjet printing is a printing technology that has brought an innovative change after the existing high-noise impact type dot matrix printer. It is the art of forming an image in Since a very small amount of fluid is sprayed on the desired point and space by a digital signal, it has the advantage of being able to freely direct-write various shapes designed in the virtual space of the computer. In addition, since the fluid is deposited from the substrate in a non-contact manner, shapes can be freely printed on various substrates such as paper, textiles, metals, ceramics, and polymers, and large areas ranging from tens of micrometers to more than several square meters are possible. .

Inkjet printing does not require processes such as development and etching required in existing patterning technologies such as photolithography, so there is no case of denaturing the properties of the substrate or material due to chemical influence, and it is very eco-friendly because there is no waste in the process It is a unique patterning technique. In addition, the pattern on demand process that can pattern as many materials as needed is possible, making it possible to produce fine patterns in an extremely simple process, so that the material utilization efficiency is close to 100%, and expensive vacuum equipment is not required. It has the advantage of being very competitive in product price due to cost reduction because it does not require any cost. Due to the superiority of inkjet printing technology, applied research is being actively carried out in fields such as displays, electronic circuits, MEMS (Micro Electro Mechanical Systems), and biochips that require tens of μm pattern processing as well as application as document printing technology. have.

The inkjet printing system can realize all colors through the four primary colors (CMYK; Cyan, Magenta, Yellow, and blacK), and it is possible to produce various product groups even under the mass production system by patterning through digital files. In comparison, the process time is very short. In addition, the inkjet printing system has high ink efficiency by discharging ink only to a desired position by a digital signal, thereby reducing production costs.

Inkjet printing has been mainly used in the traditional printing industry, but due to the advantage of being able to deposit a desired material in a non-contact method, industrial applications are gradually expanding in recent years.

Inkjet 3D printing method is a method of producing a two-dimensional section by directly discharging a material manufactured in the form of ink. It has a distinctive feature from other 3D printing methods, so it can be said to be a technology with great potential for the 3D stacking process.

Inkjet print heads have hundreds or thousands of nozzles per printhead, and each nozzle can be precisely and individually controlled, allowing multiple printheads to print multiple materials simultaneously in the same inkjet system. Inkjet printing is ideal for printing electronic products such as printed circuit boards (PCBs) because these advantages allow printing of insulating substrates along with conductors.

Republic of Korea Patent Publication No. 10-2019-0098364

An object of the present invention is to provide a photocurable ceramic composite ink composition capable of forming an insulating layer of a printed circuit board using inkjet 3D printing, and a method of manufacturing a printed circuit board using the same.

The present invention is a photocurable ceramic composite ink composition for forming the insulating layer by inkjet 3D printing to form an insulating layer formed under the conductor line of a printed circuit board, SiO ₂ sol 2-45 wt. %; 1-20 wt% of at least one oxide nanoparticle selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ; 50-90 wt% of monomer; 0.1 to 6 wt% of a surface modifier; And it provides a photocurable ceramic composite ink composition comprising 0.01 to 3wt% of a photoinitiator.

The SiO ₂ sol preferably contains silica nanoparticles having an average particle diameter of 10 to 300 nm.

The monomer may include 1,6-hexanediol diacrylate (HDDA).

The surface modifier may include 3-Mercaptopropyl (MPTMS) trimethoxy silane).

The photoinitiator may include phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

In addition, the present invention, SiO ₂ sol 2-45 wt%; 1-20 wt% of at least one oxide nanoparticle selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ; 50-90 wt% of monomer; 0.1 to 6 wt% of a surface modifier; and forming a photocurable ceramic composite ink composition comprising 0.01 to 3 wt% of a photoinitiator, and inkjet 3D printing of the photocurable ceramic composite ink composition on a substrate for forming a printed circuit board; Forming an insulating layer by photocuring the photocurable ceramic composite ink composition using a UV (Ultraviolet ray) curing machine, inkjet 3D printing and annealing the conductive ink on the insulating layer, and photosintering the annealed result to provide a method of manufacturing a printed circuit board comprising the step of forming a conductor line.

The SiO ₂ sol preferably contains silica nanoparticles having an average particle diameter of 10 to 300 nm.

The monomer may include 1,6-hexanediol diacrylate (HDDA).

The surface modifier may include 3-Mercaptopropyl (MPTMS) trimethoxy silane).

The photoinitiator may include phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

The conductive ink may be formed by adding 5 to 35 wt% of copper nanoparticles, 60 to 90 wt% of diethylene glycol monomethyl eth (DEG) and 0.1 to 7 wt% of polyvinylpyrrolidone (PVP) to a solvent and stirring.

It is preferable that the optical sintering uses an intense pulsed light (IPL) optical sintering method.

The optical sintering is preferably performed by intense pulsed light (IPL) optical sintering under a driving voltage higher than 700V.

According to the present invention, an insulating layer of a printed circuit board can be easily formed using inkjet 3D printing. In addition, a printed circuit board can be easily formed.

In addition, according to the present invention, by using a silica sol containing silica nanoparticles, it has resistance to gas and moisture while maintaining electrical properties, resistance to scratches and abrasion, thermal stability and transparency. In addition, as a diffusion aid in the photopolymerization process, it contributes to the curing reaction rate by controlling the path of the UV laser by partial scattering.

In addition, according to the present invention, a printed circuit board can be easily manufactured using an inkjet 3D (3 dimensional) printing technology that produces a three-dimensional shape by repeatedly laminating a desired material in a two-dimensional section from digital data designed in three dimensions. can be manufactured. Design and modification are very free, consume less material than conventional cutting, and unnecessary manufacturing process can be omitted, which greatly reduces manufacturing process cost and time.

Copper is easily oxidized at room temperature and has a disadvantage in that it is difficult to form an electrode such as re-oxidation occurs when sintered by a method such as thermal sintering. According to the present invention, IPL (Intense pulsed light) light using a xenon lamp By using the sintering method, there is an advantage in that the oxide film of copper can be removed by sintering the copper nanoparticles on which the oxide film is formed within a few milliseconds at room temperature and atmospheric pressure conditions.

1 is a view showing a method of synthesizing a photocurable ceramic composite ink according to an experimental example.
2 is a view showing conditions for inkjet 3D printing of the photocurable ceramic composite ink according to the experimental example.
3A and 3B are diagrams for calculating the lamination matching ratio of the photocurable ceramic composite ink according to an experimental example.
4 is a photocurable ceramic composite ink inkjet 3D printed and UV cured on a quartz plate to form an insulating layer (photocurable insulating layer), and conductive ink is inkjet printed and sintered on the insulating layer to form a conductor It is a diagram showing a state in which a line (micro circuit pattern) is formed.
5 is a view showing XRD (X-ray diffraction) peaks according to the driving voltage of the IPL optical sintering.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. However, the following examples are provided so that those of ordinary skill in the art can fully understand the present invention, and can be modified in various other forms, and the scope of the present invention is limited to the examples described below it's not going to be

When it is said that any one component "includes" another component in the detailed description or claims of the invention, it is not construed as being limited to only the component unless otherwise stated, and other components are further added. It should be understood as being able to include

In addition, 'nanoparticles' hereinafter is used to mean particles having a size of 1 nm or more and less than 1 μm as particles in nanometer (nm) units.

The photocurable ceramic composite ink composition according to a preferred embodiment of the present invention is a photocurable ceramic composite ink composition that forms the insulating layer by inkjet 3D printing to form an insulating layer formed under the conductor line of a printed circuit board A ceramic composite ink composition comprising: 2 to 45 wt% of a SiO ₂ sol; 1-20 wt% of at least one oxide nanoparticle selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ; 50-90 wt% of monomer; 0.1 to 6 wt% of a surface modifier; and 0.01 to 3 wt% of a photoinitiator.

The SiO ₂ sol preferably contains silica nanoparticles having an average particle diameter of 10 to 300 nm.

The monomer may include 1,6-hexanediol diacrylate (HDDA).

The surface modifier may include 3-Mercaptopropyl (MPTMS) trimethoxy silane).

The photoinitiator may include phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

A method of manufacturing a printed circuit board according to a preferred embodiment of the present invention, SiO ₂ Sol 2 to 45 wt%; 1-20 wt% of at least one oxide nanoparticle selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ; 50-90 wt% of monomer; 0.1 to 6 wt% of a surface modifier; and forming a photocurable ceramic composite ink composition comprising 0.01 to 3 wt% of a photoinitiator, and inkjet 3D printing of the photocurable ceramic composite ink composition on a substrate for forming a printed circuit board; Forming an insulating layer by photocuring the photocurable ceramic composite ink composition using a UV (Ultraviolet ray) curing machine, inkjet 3D printing and annealing the conductive ink on the insulating layer, and photosintering the annealed result to form a conductor line.

The SiO ₂ sol preferably contains silica nanoparticles having an average particle diameter of 10 to 300 nm.

The monomer may include 1,6-hexanediol diacrylate (HDDA).

The surface modifier may include 3-Mercaptopropyl (MPTMS) trimethoxy silane).

The photoinitiator may include phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

The conductive ink may be formed by adding 5 to 35 wt% of copper nanoparticles, 60 to 90 wt% of diethylene glycol monomethyl eth (DEG) and 0.1 to 7 wt% of polyvinylpyrrolidone (PVP) to a solvent and stirring.

It is preferable that the optical sintering uses an intense pulsed light (IPL) optical sintering method.

The optical sintering is preferably performed by intense pulsed light (IPL) optical sintering under a driving voltage higher than 700V.

Hereinafter, a photocurable ceramic composite ink composition according to a preferred embodiment of the present invention will be described in more detail.

The photocurable ceramic composite ink composition according to a preferred embodiment of the present invention is a photocurable ceramic composite ink composition that forms the insulating layer by inkjet 3D printing to form an insulating layer formed under the conductor line of a printed circuit board A ceramic composite ink composition.

The photocurable ceramic composite ink composition according to a preferred embodiment of the present invention comprises a SiO ₂ sol, BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ It includes one or more oxide nanoparticles selected from the group consisting of Ti ₄ O ₁₂ , a monomer, a surface modifier, and a photoinitiator.

The SiO ₂ sol is preferably contained in an amount of 2 to 45 wt% in the photocurable ceramic composite ink composition. The SiO ₂ sol preferably contains silica (SiO ₂ ) nanoparticles having an average particle diameter of 10-500 nm, more preferably 10-300 nm. By containing silica nanoparticles, it has resistance to gas and moisture while maintaining electrical properties, resistance to scratches and abrasion, thermal stability and transparency. In addition, as a diffusion aid in the photopolymerization process, it contributes to the curing reaction rate by controlling the path of the UV laser by partial scattering.

The oxide nanoparticles are preferably oxides having dielectric properties. The oxide nanoparticles include one or more nanoparticles selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ . may include The oxide nanoparticles are preferably contained in an amount of 1 to 20 wt% in the photocurable ceramic composite ink composition. The oxide nanoparticles are preferably nanoparticles having an average particle diameter of 10-500 nm, more preferably 10-300 nm. The oxide nanoparticles may serve to increase insulation and improve the resistance of the insulation layer when the insulation layer of the printed circuit board is formed.

The monomer is preferably contained in an amount of 50 to 90 wt% in the photocurable ceramic composite ink composition. The monomer may include 1,6-hexanediol diacrylate (HDDA).

The surface modifier is preferably contained in an amount of 0.1 to 6 wt% in the photocurable ceramic composite ink composition. The surface modifier may include 3-Mercaptopropyl (MPTMS) trimethoxy silane).

The photoinitiator is preferably contained in an amount of 0.01 to 3 wt% in the photocurable ceramic composite ink composition. The photoinitiator may include phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

Hereinafter, a method of manufacturing a printed circuit board according to a preferred embodiment of the present invention will be described in more detail.

A photocurable ceramic composite ink composition is formed to form an insulating layer formed under the conductor line of a printed circuit board.

The photocurable ceramic composite ink composition includes a SiO ₂ sol, BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ A group consisting of It includes one or more oxide nanoparticles selected from, a monomer, a surface modifier, and a photoinitiator.

The SiO ₂ sol is preferably contained in an amount of 2 to 45 wt% in the photocurable ceramic composite ink composition. The SiO ₂ sol preferably contains silica (SiO ₂ ) nanoparticles having an average particle diameter of 10-500 nm, more preferably 10-300 nm. By containing silica nanoparticles, it has resistance to gas and moisture while maintaining electrical properties, resistance to scratches and abrasion, thermal stability and transparency. In addition, as a diffusion aid in the photopolymerization process, it contributes to the curing reaction rate by controlling the path of the UV laser by partial scattering. The photopolymerization method has the characteristics that the polymerization reaction proceeds into a solid polymer in a very short time, the reaction is possible even at low energy, and has the advantages of controlling the flexibility and surface properties of the substrate. Because of these advantages, photopolymerization can be very actively used in film, coating, ink, adhesive and 3D printing processes.

The oxide nanoparticles are preferably oxides having dielectric properties. The oxide nanoparticles include one or more nanoparticles selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Pa(Zr,Ti)O ₃ , (Pb,La)(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ . may include The oxide nanoparticles are preferably contained in an amount of 1 to 20 wt% in the photocurable ceramic composite ink composition. The oxide nanoparticles are preferably nanoparticles having an average particle diameter of 10-500 nm, more preferably 10-300 nm. The oxide nanoparticles may serve to increase insulation and improve the resistance of the insulation layer when the insulation layer of the printed circuit board is formed.

The monomer is preferably contained in an amount of 50 to 90 wt% in the photocurable ceramic composite ink composition. The monomer may include 1,6-hexanediol diacrylate (HDDA).

The surface modifier is preferably contained in an amount of 0.1 to 6 wt% in the photocurable ceramic composite ink composition. The surface modifier may include 3-Mercaptopropyl (MPTMS) trimethoxy silane).

The photoinitiator is preferably contained in an amount of 0.01 to 3 wt% in the photocurable ceramic composite ink composition. The photoinitiator may include phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

The photocurable ceramic composite ink composition is inkjet 3D printed on a substrate for forming a printed circuit board.

An insulating layer is formed by photocuring the photocurable ceramic composite ink composition using an Ultraviolet ray (UV) curing machine. The insulating layer of the printed circuit board may be formed by inkjet 3D printing of the photocurable ceramic composite ink and then photopolymerization using an ultraviolet ray (UV) laser.

Conductive ink is inkjet 3D printed on the insulating layer and annealed. The conductive ink may be formed by adding 5 to 35 wt% of copper nanoparticles, 60 to 90 wt% of diethylene glycol monomethyl eth (DEG) and 0.1 to 7 wt% of polyvinylpyrrolidone (PVP) to a solvent and stirring. The copper nanoparticles are preferably nanoparticles having an average particle diameter of 10-500 nm, more preferably 10-300 nm. The solvent may be an alcohol such as ethanol or methanol. The annealing is preferably performed at a temperature of about 80 to 200° C. lower than the boiling point of PVP.

The annealed product is optically sintered to form a conductor line. It is preferable that the optical sintering uses an intense pulsed light (IPL) optical sintering method. In the manufacture of conductive ink, electrical conductivity, thermal stability, mechanical and electrical reliability, sintering efficiency, etc. are required. For this reason, noble metals such as gold (Au), silver (Ag), and platinum (Pt) have been mainly used, but these are disadvantageous in that they are not economical in terms of cost. Therefore, a conductive ink containing copper nanoparticles is used to replace it. However, most copper is easily oxidized at room temperature and has a disadvantage in that it is difficult to form an electrode, such as re-oxidation when sintered by a method such as thermal sintering. In order to overcome this, it is preferable to use an Intense Pulsed Light (IPL) optical sintering method using a xenon lamp. The IPL optical sintering has an advantage in that the oxide film of copper can be removed by sintering the copper nanoparticles on which the oxide film is formed within a few milliseconds at room temperature and atmospheric pressure.

The optical sintering is preferably performed by intense pulsed light (IPL) optical sintering under a driving voltage higher than 700V. When the driving voltage is less than 700V, copper oxide (Cu ₂ O) may be present in the conductor line, and thus resistance may increase. According to an experimental example to be described later, when the driving voltage of IPL optical sintering is less than 700 V, copper oxide (Cu ₂ O) is present in the conductor line, and when the driving voltage of IPL optical sintering is 700 V or more, copper oxide ( Cu ₂ O) was not present, and the IPL optical sintering at a driving voltage of less than 700 V showed a lower resistance than that of the case.

Hereinafter, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the experimental examples presented below.

<Experimental example>

In the experimental example of the present invention, it was attempted to manufacture a printed circuit board (PCB) using inkjet 3D printing technology.

For the insulating layer of the printed circuit board, an insulating pattern (insulating layer) was formed by photopolymerization using a UV (ultraviolet ray) laser having a wavelength of about 385 nm by manufacturing a photocurable ceramic composite ink. The photocurable ceramic composite ink includes a silica (SiO ₂ ) sol, BaTiO ₃ nanoparticles, a monomer, a surface modifier, and a photoinitiator. The silica (SiO ₂ ) sol contains silica nanoparticles, and by adding silica nanoparticles, it has resistance to gas and moisture while maintaining electrical properties, resistance to scratches and abrasion, thermal stability and transparency. In addition, as a diffusion aid in the photopolymerization process, it contributes to the curing reaction rate by controlling the path of the UV laser by partial scattering. The photopolymerization method has the characteristics that the polymerization reaction proceeds into a solid polymer in a very short time, the reaction is possible even at low energy, and has the advantages of controlling the flexibility and surface properties of the substrate. Because of these advantages, photopolymerization can be very actively used in film, coating, ink, adhesive and 3D printing processes.

Table 1 below shows the composition ratio (unit: wt%) of the components for synthesizing the photocurable ceramic composite ink (A, B, C, D, E ink).

SiO ₂ sol
(D90: 90nm) BaTiO ₃ nanoparticles
(D90: 150nm) monomer surface modifier photoinitiator A ink 10 0 88.1 One 0.9 B ink 20 0 77.2 2 0.8 C ink 30 0 66.3 3 0.7 D ink 15 5 77.2 2 0.8 E ink 10 10 77.2 2 0.8

In this experimental example, the SiO ₂ sol containing silica nanoparticles having an average particle size of 90 nm was used, and the BaTiO ₃ nanoparticles having an average particle size of 150 nm were used. In this experimental example, 1,6-hexanediol diacrylate (HDDA) was used as the monomer, the surface modifier (silane coupling) was MPTMS (3-Mercaptopropyl) trimethoxy silane), and the photo initiator was phenylbis. (2,4,6-trimethylbenzoyl)-phosphine oxide (phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide) was used.

1 shows a method of synthesizing a photocurable ceramic composite ink according to an experimental example.

Referring to FIG. 1, SiO ₂ sol, BaTiO ₃ nanoparticles and a surface modifier are mixed, stirred at 50° C. at 300 rpm for 24 hours to hydrolyze, and a monomer is added and mixed for 3 hours, and then a photoinitiator was added and sonicated for 10 minutes to synthesize a photocurable ceramic composite ink.

An experiment was conducted using a Dropwatcher (Cera DW, STI) to form an insulating layer by printing the photo-curable ceramic composite ink on a quartz plate. Inkjet 3D printing conditions of the photocurable ceramic composite ink for forming an insulating layer on the quartz plate are shown in FIG. 2 .

Referring to FIG. 2 , the inkjet 3D printing driving conditions are set at a temperature of 25° C. with a driving voltage of 68V, a rising time of 1.3 μs, a dwell time of 4.6 μs, and a falling time. was set to 1.3 μs, delay time was set to 1 μs, and D2D (drop to drop) was set to 300. In the case of a UV (Ultraviolet ray) curing machine that cures ejected droplets (droplets of photocurable ceramic composite ink), a UV light source with a wavelength of 385 nm was used, and the amount of light was set to 7W/cm ² , and the exposure time was set to 1.2s.

a) Rising time: 1.3㎲

b) Dwell time: 4.6㎲

c) Falling time: 1.3㎲

d) Delay time: 1㎲

e) Voltage: 68.0V

f) D2D: 300

e) UV LED curing: 385nm

After printing the photocurable ceramic composite inks (A, B, C, D, E inks) synthesized according to the experimental example in a size of 5 mm × 5 mm, the conversion rate, the lamination match rate, and the resistance were measured and shown in Table 2 below. It was.

Ink A B C D E Conversion rate (%) 48 69 52 68 58 Lamination match rate (%) 73.6 93.5 88.5 92.3 88.2 Resistance (Ω cm) 2.43×10 ¹² 6.43×10 ¹² 8.43×10 ¹² 2.43×10 ¹³ 4.52×10 ¹³

The lamination agreement rate was calculated by extracting a digital file of the 3D laminate (see FIG. 3b ) with a scanner and calculating the agreement rate with the original drawing (size of 5 mm×5 mm) (see FIG. 3a ).

After inkjet 3D printing of a photocurable ceramic composite ink on a quartz plate and UV curing to form an insulating layer, a conductive ink (Copper nanoink) was prepared for realizing the line width of a microcircuit, and the Inkjet 3D printing was performed on the insulating layer, annealed at 100° C. for 1 hour, and then sintered to form a conductor line. 4 is a photocurable ceramic composite ink inkjet 3D printed and UV cured on a quartz plate to form an insulating layer (photocurable insulating layer), and conductive ink is inkjet printed and sintered on the insulating layer to form a conductor It is a diagram showing a state in which a line (micro circuit pattern) is formed.

The conductive ink was formed by adding 20 wt% of copper nanoparticles, 78 wt% of DEG (Diethylene glycol monomethyl eth) and 2 wt% of PVP (Polyvinylpyrrolidone) to ethanol as a solvent and stirring at 25° C. at 400 rpm for 12 hours. As the copper nanoparticles, those having an average particle diameter of 100 nm were used. As the PVP, a molecular weight of about 40,000 was used.

In the manufacture of conductive ink, electrical conductivity, thermal stability, mechanical and electrical reliability, sintering efficiency, etc. are required. For this reason, noble metals such as gold (Au), silver (Ag), and platinum (Pt) have been mainly used, but these are disadvantageous in that they are not economical in terms of cost. Therefore, copper nano-ink was used to replace it. However, most copper is easily oxidized at room temperature and has a disadvantage in that it is difficult to form an electrode, such as re-oxidation when sintered by a method such as thermal sintering. In order to overcome this problem, IPL (Intense pulsed light) optical sintering method using a xenon lamp was used, which sintered the copper nanoparticles formed with the oxide film within a few milliseconds at room temperature and atmospheric pressure condition to sinter the copper oxide film. The advantage is that it can be removed.

Optical sintering (IPL optical sintering) was performed on the inkjet 3D printed copper nanoink on the insulating layer to form a conductor line. The optical sintering has an advantage in that the oxide film of copper contained in the copper nano-ink can be removed.

The photosintering conditions are shown below.

a) Voltage(V): 400∼800V

b) On time (ms): 10

c) Frequency (Hz): 1

d) Off time (ms): 90

e) Pulse number: 1

f) Z: 5mm

5 is a diagram showing XRD (X-ray diffraction) peaks according to the driving voltage of IPL optical sintering.

Referring to FIG. 5 , the optical sintering driving condition was carried out at a driving voltage of 400 to 800 V under atmospheric pressure and room temperature conditions, and as the driving voltage increased, the XRD (X-ray diffraction) peak value of copper oxide decreased. could check When the driving voltage was less than 700V, a peak of copper oxide (Cu ₂ O) existed, but when the driving voltage of the IPL optical sintering was 700 V or more, a peak of copper oxide (Cu ₂ O) did not appear.

After inkjet 3D printing of ink B (photocurable ceramic composite ink) shown in Table 1 on a quartz plate and UV curing to form an insulating layer, inkjet 3D printing of conductive ink on the insulating layer and IPL The resistance of the conductor line formed by photosintering is shown in Table 3 below.

Voltage
(V) 400 500 600 700 800 Resistance (μΩ cm) 8350 6359 2132 432 362

Referring to Table 3, it was confirmed that the resistance decreased as the driving voltage of the IPL optical sintering increased to 400, 500, 600, 700, and 800 V.

A, B, C, D, E inks (photocurable ceramic composite ink) shown in Table 1 were inkjet 3D printed on a quartz plate and UV cured to form an insulating layer, and then Table 4 below shows the resistance of the conductor lines formed by inkjet 3D printing of conductive ink and IPL optical sintering at a driving voltage of 800V.

Voltage
(V) A B C D E Resistance (μΩ cm) 348 362 376 298 291

Referring to Table 4, it was found that the resistance was lower in the case of using the D and E inks in which BaTiO ₃ was used compared to the cases in which the A, B, and C inks in which BaTiO ₃ was not used were used.

As mentioned above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications are possible by those skilled in the art.

Claims (13)

A photocurable ceramic composite ink composition for forming the insulating layer by inkjet 3D printing to form an insulating layer formed under a conductor line of a printed circuit board,
SiO ₂ sol 2-45 wt%;
1-20 wt% of one or more oxide nanoparticles selected from the group consisting of SrTiO ₃ , Pa(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ;
50-90 wt% of monomer;
0.1 to 6 wt% of a surface modifier; and
A photocurable ceramic composite ink composition comprising 0.01 to 3 wt% of a photoinitiator.
The photocurable ceramic composite ink composition according to claim 1, wherein the SiO ₂ sol contains silica nanoparticles having an average particle diameter of 10 to 300 nm.
The photocurable ceramic composite ink composition of claim 1, wherein the monomer comprises 1,6-hexanediol diacrylate (HDDA).
The photocurable ceramic composite ink composition of claim 1, wherein the surface modifier comprises 3-Mercaptopropyl (MPTMS) trimethoxy silane).
The photocurable ceramic of claim 1, wherein the photoinitiator comprises phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide. Composite ink composition.
SiO ₂ sol 2-45 wt%;
1-20 wt% of one or more oxide nanoparticles selected from the group consisting of SrTiO ₃ , Pa(Zr,Ti)O ₃ and CaCu ₃ Ti ₄ O ₁₂ ;
50-90 wt% of monomer;
0.1 to 6 wt% of a surface modifier; and
forming a photocurable ceramic composite ink composition comprising 0.01 to 3 wt% of a photoinitiator;
Inkjet 3D printing the photocurable ceramic composite ink composition on a substrate for forming a printed circuit board (Printed Circuit Board);
forming an insulating layer by photocuring the photocurable ceramic composite ink composition using an Ultraviolet ray (UV) curing machine;
3D printing and annealing the conductive ink on the insulating layer; and
A method of manufacturing a printed circuit board, comprising the step of forming a conductor line by optically sintering the annealed product.
The method of claim 6, wherein the SiO ₂ sol contains silica nanoparticles having an average particle diameter of 10 to 300 nm.
The method of claim 6 , wherein the monomer comprises 1,6-hexanediol diacrylate (HDDA).
The method of claim 6 , wherein the surface modifier comprises 3-Mercaptopropyl (MPTMS) trimethoxy silane).
The printed circuit board of claim 6 , wherein the photoinitiator comprises phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide. manufacturing method.
The method according to claim 6, wherein the conductive ink is formed by adding 5 to 35 wt% of copper nanoparticles, 60 to 90 wt% of DEG (Diethylene glycol monomethyl eth), and 0.1 to 7 wt% of PVP (Polyvinylpyrrolidone) to a solvent and stirring. A method for manufacturing a printed circuit board.
The method of claim 6 , wherein the optical sintering is performed using an intense pulsed light (IPL) optical sintering method.
The method of claim 12 , wherein the optical sintering is performed by intense pulsed light (IPL) optical sintering under a driving voltage higher than 700V.

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