KR101272029B1 - Method for Preparing the Photo Curable Inkjet Ink Formulation Usable In 3D Inkjet Printing System for Electric or Electron Materials - Google Patents

Abstract

The present invention relates to an ink composition for an electrical material or an electronic material having anisotropy capable of inkjet printing using a photocurable inkjet printing system, and specifically, an electromagnetic conductive rheological polymer ink composition and a natural organic light emitting phosphorescent (fluorescent) ink composition. And it relates to a method of manufacturing all electrical materials or electronic components using the same. The present invention comprises the steps of selecting a salt-peel phosphor (fluorescent); Preparing electromagnetic conductive polymer particles; Preparing a photocurable dispersion master solution comprising an electromagnetic conductive polymer or a salt-pigment phosphor; Milling and dispersing the photocurable dispersion master solution; And mixing and dispersing the dispersed photocurable dispersion master solution and the photoreaction chemical, and precisely filtering the photocurable ink composition for all electrical or electronic materials.

Description

Method for preparing the Photo Curable Inkjet Ink Formulation Usable In 3D Inkjet Printing System for Electric or Electron Materials}

The present invention relates to an ink composition for an electrical or electronic material having anisotropy and electromagnetic conductivity capable of inkjet printing using a photocurable inkjet printing system, and in particular, an electrically conductive rheological polymer ink composition and a natural organic light emitting phosphorescent (fluorescence). The present invention relates to a body ink composition and a method for manufacturing an electrical or electronic component using the same.

Solvent-type UV curing inks that can use inkjet printing in the field of manufacturing flexible electronic materials have attracted attention. In general, the inkjet printing method can be generally divided into a direct printing method and a thermal transfer printing method by a thermal transfer system by transferring to paper. Photocuring inkjet printing is environmentally friendly due to simple process equipment and no waste water since no additional process for washing and fixing is required.

However, even in the existing digital printing system, it is difficult to completely prevent the generation of hazardous chemicals depending on the type of the ink composition. Looking at the harmful substances that occur in digital sublimation transcription systems and petroleum solvent dilution UV curing systems as digital print systems, the US Food and Drug Agency (FDA) has identified sulfonated lignin, formaldehyde, N, Approximately 5,000 hazardous chemicals such as N-dimethylformamide, dimethyl sulfoxide, hydrazine, and morpholine are defined as observing or toxic substances. EPA (Environmental Protection Agency) includes acetonitrile, dimethyl sulfate, dimethylolamine, ethanolamine, N, N-dimethylformamide, formaldehyde, hydrazine, About 10,000 chemicals, such as methyl ethyl ketone and triethylamine, are classified and managed as hazardous organic volatile and water air pollutants. The International Chemical Safety Card also includes Acetonitrile, Dimethyl Sulfate, Dimethyl Sulfoxide (DMSO), Ethanolamine, N, N-Dimethylform Dimethylformamide, formaldehyde, hydrazine, morpholine (Morpholine), methyl ethyl ketone, sodium hydroxide (NaOH), tetrahydrofuran (THF) and urea as hazardous chemicals Doing. In addition, the Korea National Institute of Environmental Science defines methyl ethyl ketone, trimethyl amine, ethyl acetate, hydrazine, sodium hydroxide, dimethyl sulfate and formaldehyde as hazardous substances.

The harmful organic solvent is used to improve the output quality of the ink in the inkjet printing process. Specifically, organic solvents containing such harmful chemicals are used to make emulsion solutions in which the monodispersity and pigment particles have high stability. However, the use of the solvent not only has a detrimental effect on the worker in the working process but also can generate harmful organic volatiles and water pollutants due to by-products of the process.

In order to replace this, UV curing system, which is a direct printing method, is adopted.However, due to the increase in system price and maintenance cost of the device, the UV curing system is used in the electronic, electrical, shipbuilding, It is not suitable as a system of digital inkjet inks for flexible materials as a system for special applications such as automobiles and aerospace. Conventional digital electronic ink has a disadvantage that a specific pigment, dye phosphor (fluorescent) should be used because dyes and pigments (inks) are dyed (adhered) to the material by a dyeing mechanism, which has been pointed out in WO2007005240.

The current digital electronic printing process is easier to print using the digital electronic printing system than the conventional screen electronic printing process, but the pre-treatment process of the material for preventing ink bleeding and improving pigment-dye adhesion is still possible. Due to its complexity, it is known to be the biggest obstacle to the expansion of digital printing process. Recently, developed countries and overseas dye and pigment manufacturers are actively researching ink for digital electronic printing, which is available for all kinds of materials, but commercialized products are not known as an early stage of research and development.

Accordingly, an object of the present invention is to provide a photocurable ink composition for an electric material or an electronic material that can compensate for the disadvantages while applying the photocuring system of the existing dyes and pigments.

The ink composition of the present invention is physicochemically stable and can be applied to various kinds of materials such as films, glass and wood, and does not require pre and post treatment. In the existing screen electronic printing process, a pre- and post-treatment process according to the material is essential to obtain an optimal printed material. Existing screen electronic printing process requires complicated processes such as vacuum decompression plasma surface treatment-thin film coating-print-exposure-etching-depressurization heating-washing-drying-bonding-molding-insulation process of silicon wafer and material surface processing. Water pollution occurs due to the chemicals used in the pretreatment and post-treatment processes, and environmental problems are caused by unfixed reaction dye pigments and unremoved pretreatment materials after printing on the material.

In the screen electronic printing in the precision electronics industry, liquid crystal display (LCD), thin film transistor-liquid crystal display (TFT-LCD), plasma display (PDP), set-off field emission display (SED) and FED are mainly used. (Field Emission (Emitting) Display), OLED (Organic Limiting Emission Display), AMOLED (Active Matrix Organic Limiting Emission Display), PLED (Inorganic Phosphorus Organic Limiting Emission Display), Polymer-OLED (Polymer-Organic Limiting Emission Display), OTFT It is used for display materials such as LCD (Organic Thin Film Transistor- Liquid Crystal Display), E-paper, Laser Paper (LCD). In this case, chemically modified polyvinyl vinylene (PPV) -based or polyvinyl vinyl carbazole (PVK) -based conductive polymers are printed and electronic components are cleaned or surface-treated. In this process, organic volatile compounds (ethanol, benzene Etc.) are used or generated and the process is very complicated. In addition, carbon structuring materials such as carbon nanotubes, polypyrrole, and graphite are used to solve the switching problem of the liquid crystal, but problems of transparency, dispersion, and coating still exist. In addition, an attempt was made to use an electrochromic polymer, but in the case of an electrochromic material, there is a problem in that luminous efficiency rapidly decreases with time. In addition, in the case of the low molecular phosphors entering the organic light emitting display, the luminous efficiency decreases with time, and the phosphor (fluorescent) used in the conventional LCD also has the disadvantage that the thickness of the display itself when used in the organic light emitting display.

The present invention provides a method for preparing an aqueous based or vegetable oil based photocurable inkjet ink composition which does not emit harmful substances and has a super high resolution similar to electron silver salt photographs for a conventional display, and does not emit harmful substances and can be used in various inkjet heads. to provide. Specifically, the present invention provides a method of manufacturing a high-performance polymer inkjet ink having an electroconductive rheological property including a material used for liquid crystal, and using the same, to realize a precision electrical and electronic component using a three-dimensional photocurable inkjet large format digital printer. To provide.

In order to solve the above problems, according to a preferred embodiment of the present invention, preparing an electromagnetic conductive polymer particles; Preparing a photocurable dispersion master solution including the electromagnetic conductive polymer; Milling and dispersing the photocurable dispersion master solution; And mixing and dispersing the dispersed photocurable dispersion master solution and the photoreaction chemical, and finely filtering the photocurable ink composition for electrical and electronic materials.

According to another suitable embodiment of the present invention, the step of preparing the electromagnetic conductive polymer particles may be a polystyrene-acrylate-thiophene-acene-aniline-methylmethacrylate-unsaturated polyester mixture,

Placing the modified silicone fluorinated-unsaturated polyester mixture in an ultrapure water or vegetable oil mixture and then polymerizing in the presence of a solvent and a catalyst; Synthesizing an electromagnetic conductive polymer by adding aluminum oxide and calcium hydrate to the polymer; Crystallizing the polymer by adding it to an azeotrope mixed with isopropyl alcohol and ethyl alcohol at 20:80 (volume ratio);

Electromagnetic conductive polymer particles are prepared by adding the crystallized polymer, an initiator, a photosensitizer, a styrene / acrylate / methylmethacrylate / polyethyl-propyloxide mixture, a modified silicone / fluoro copolymer, an electrochromic material and an inorganic substance. It includes a step.

According to another suitable embodiment of the present invention, the method comprises the steps of selecting a dye or pigment phosphor (fluorescent); Preparing a photocurable dispersion master solution comprising the dye or pigment phosphor (fluorescent); Milling and dispersing the photocurable dispersion master solution; And mixing and dispersing the dispersed photocurable dispersion master solution and the photoreaction chemical, and finely filtering the photocurable ink composition for electrical and electronic materials.

According to another suitable embodiment of the present invention, the photocured dispersion master solution comprises the steps of mixing the ultrapure water or vegetable oil mixture with a surfactant; The polythiophenephosphonate-methyl methacrylate-modified unsaturated polyester copolymer polymer or polystyrene phosphonate-methyl methacrylate-modified unsaturated polyester copolymer polymer, modified fluorinated silicone polymer and conductive polymer are added to the mixture. Preparing a dispersion solution; And adding the conductive polymer particles or the dye-pigment phosphor (fluorescent substance) to the polymer dispersion solution and dispersing the mixture with stirring to produce a photocurable ink composition for electric and electronic materials. to provide.

According to another suitable embodiment of the present invention, the photocurable ink composition for electrical and electronic materials is 14 to 28% by weight of the photocurable dispersion master solution, 60 to 80% by weight of water or vegetable oil mixture, pH buffer 0.1-1% by weight solution, 3-6% by weight photocuring monomer, 0.1-1% by weight surface tension modifier, at least one 0.1-1% by weight selected from the group consisting of photoinitiators, thermal initiators and free radical initiators, sensitizer 0.1 ~ 5% by weight, 0.1 to 1% by weight of the collecting agent, 0.1 to 1% by weight stabilizer, 0.1 to 1% by weight of the antifoaming agent and 0.5 to 1% by weight of the moisturizing agent.

According to still another preferred embodiment of the present invention, there is provided an electrical and electronic component manufactured by printing with a three-dimensional digital printer using the photocurable ink composition for electrical and electronic materials.

The ink composition prepared by the present invention can be used for various types of heads without using harmful chemicals. In addition, the ink composition of the present invention does not discharge harmful chemicals in the curing process does not have a harmful effect on the operator and the environment and can be used for various types of head, not a limited type of head. Furthermore, 3D photocurable inkjet printers can be used to manufacture lighter and thinner precision electronic components, maximizing power consumption and power production efficiency. The ink prepared in the present invention can be used in precision electrical and electronic components such as secondary cells, solar cells, fuel cells, integrated circuits, high integrated circuits, ultra high integrated circuits, chemical sensors, DNA chips, electromagnetic shielding, and the like.

1 schematically illustrates a manufacturing process of a photocurable inkjet ink composition comprising a dye, a pigment phosphor (fluorescent) body and electromagnetic conductive rheological polymer particles according to the present invention.
2 is a block diagram showing the overall hardware configuration of a three-dimensional printing system according to an embodiment of the present invention.
FIG. 3 illustrates parallel processing operations of software by the three-dimensional printing system shown in FIG. 2.
4A shows a typical liquid crystal display.
4B illustrates a liquid crystal display that is an example of an electronic product made by the method of the present invention.
FIG. 5 shows the color range of the display (red) which is an electronic product manufactured by the method of the present invention in Example 11 together with the color range of NTSC (violet), Adobe RGB (yellow) and commercially available TFT LCD (green).

The present invention provides a photocurable ink composition for water-soluble (Red, Green, Blue, Black) or vegetable oils (Optical, White, Optical Electrode) -based electrical and electronic materials, including electromagnetic conductive rheological polymer and dyes, pigments. Conventional molten LCD liquid crystal (Thermotropic LCD) is LCP (Liquid Crystal Polymer) is formed by TN (Twist Nematic) method, in the present invention by providing an ink composition for electrical and electronic materials that can be applied to a three-dimensional optical curing printer A flexible three-dimensional photocurable printer can produce electrical and electronic components.

In the present invention, polyphenylvinylene, polyvinylcarbazole, polypyrrole, polyacetylene, polythiophene, polyacene, polyanaline, dendrimer, fullerene, carbon nanotube (CNT: Carbon Nano Tube, SWCNT, MWCNT), graphite, graphene By forming a structured Lyotropic-Thermotropic Liquid Crystal using polymers such as fins and Nano Wire, their electromagnetic rheological properties can be controlled for each color cell by an electrical signal. . As a result, the color (Red, Blue, Green) cell control in the conventional liquid crystal polymer (LCP) can not be achieved to improve the quantum electrical drive for each color cell can be implemented.

Their chemiluminescence using modified poly ethylene dioctylthiopene (PEDOT), modified poly phenylene vinylene (PPV), modified poly vinylene carbazole (PVK) and natural luciferin or luminol, which are soluble in ultrapure water or vegetable oil free of harmful substances By applying the principle, it is possible to form a large-area planarized organic-inorganic hybrid polymer-low molecular polymer light-emitting polyhedron. The problem caused by the phenomenon can be solved. In addition, the dielectric constant and efficiency can be maximized by using high dielectric materials such as iridium and hafnium to improve low efficiency, which is a disadvantage of polymer light emission. In order to compensate for the advantages of not generating heat, which is an advantage of chemical light emission, and to overcome the disadvantage of manufacturing by biodegradation, a nano-particle organic / inorganic hybrid encapsulation was used. The ink composition can be used to manufacture electrical and electronic components such as a display through a single printing process using a three-dimensional photo curing printer to escape the existing complex process.

The present invention uses a light (radiation, ultraviolet, infrared, visible light, microwave) light emitting diode curing device in the printing system to speed up the curing speed, and selected a form of moisture curing at room temperature for energy saving.

The method for producing the dispersion master stock solution of a photocurable dye, a pigment phosphorescent inkjet ink, comprises at least one dye, such as based on aqueous (red, blue, green, black) and vegetable oils (transparent, white, transparent electrodes), Selecting a pigment phosphor (fluorescent); Amphoteric (water soluble, fat soluble) photocurable modified polystyrene-acrylate-analine-acene-thiophene-methylmethacrylate-unsaturated ester photocured polymer from Sigma-Aldrich; Dyes, pigment phosphorescent (fluorescent) dyes 10 to 40 wt%; And super pure water or mixed vegetable oils (mixed dilution vegetable oils: 20 to 60 wt% vegetable oil, 20 to 40 wt% ether, 10 to 20 wt% lactam, 20 to 40 wt% lactone) 50 to 70 wt% dyes, pigment phosphorescent Preparing a (fluorescent) body dispersion solution; Preparing an ink composition stock solution in which a zirconium-silica carbide-hafnium bead of 0.02 to 5 mm is placed in a milling machine so that the average particle size of the dye and the pigment phosphorescent (fluorescent) pigment is 0.1 to 20 nm; Preparing a 0.8-30 nm sized electroconductive rheological polymer particle stock solution for Lyotropic-Thermotropic liquid crystal polymer (LCP); Preparing a photocurable oligomer or prepolymer using a light (radiation, ultraviolet, infrared, visible, microwave) reaction monomer; Adding a reaction chemical to adjust the viscosity, surface tension, viscosity, and the like to prepare an ink composition; And filtration of the ink constituents prepared, and the dye and pigment UV curable inks do not release volatile organic compounds during the curing process.

According to another suitable embodiment of the present invention, a photo-curable inkjet ink based on ultra pure water (red, blue, green, black) and mixed vegetable oil (transparent, white, transparent electrode) for inkjet electronic printing is at least one of Dispersion stock solutions comprising dyes, pigments and polystyrene / acrylate / thiophene / analine / acene / methylmethacrylate / unsaturated ester photocured polymers and modified silicone / fluoro copolymers; Ultra pure water or mixed vegetable oils; Potassium hydroxide pH buffer solution; A thickener prepared from a solution of vegetable oil mixed with water in any one or 5 to 500 ultrapure solutions thereof selected from the group consisting of polyethylene glycol and polypropylene glycol; Any or a mixture thereof selected from the group consisting of glycerin, butanediol, propanediol, and hexadiol is mixed diol solution mixed with normal methylpyrrolidone (NMP) and 2-pyrrolidone in ultra pure water or mixed vegetable oil. Including a moisturizer prepared, lignin dispersants such as sulfonic lignin, acetonitrile, dimethyl sulfate, dimethanolamine, N, N- dimethylformamide, formaldehyde, hydrazine, methyl ethyl ketone, triethylamine during the curing process It does not release dimethyl sulfoxide, morpholine, sodium hydroxide, tetrahydrofuran or urea. The photocurable inkjet ink aqueous based composition is an ink composition comprising at least one of red, blue, green, black and vegetable oil based optical, white and optical eletronodes, pigment phosphors and organic substituted metallic molecules. Silver amphoteric (water-soluble, fat-soluble) polyacrylate / polymethylmethacrylate photopolymerization oligomers; Poly ethyl-propyl oxide; Modified polysiloxane / floor organic / inorganic hybrid radical polymerization oligomers; Ethyl diacrylate, propyl diacrylate, butyl diacrylate, ethyl methacrylate, propyl methyl methacrylate, butyl methyl methacrylate, isopropyl acrylamide monomer; polyethyl methacrylate, polyethyl acrylate, unsaturated Polyester prepolymers, polyethylurea prepolymers, polyurethane prepolymers, polyurethane-acrylate prepolymers; And benzoacephenone as photoinitiator; Azobismethylpropiamidinedihydrochloride (azobismethylnitrile) as a thermal radical initiator; Benzoperoxides, which are free radical initiators; TINUV 5060,5061 from BASF (Ciba spe.) As a stabilizer; Hydroperoxide from Sigma-Aldrich as a collecting agent; As a sensitizer, dispersion master stock solution containing polycinnamate etc .; Ultra pure water or diluted mixed vegetable oils (vegetable oils, ethers, lactams, lactones); Potassium hydroxide pH buffer solution; Polyethylene glycol, polypropylene glycol; Mixed-polyethyleneglycol (M _W ) mixed with ultra pure water dilution mixed vegetable oils (vegetable oils, ethers, lactams, lactones) of any one or a mixture of 5 to 6,000 selected from the modified group consisting of 400 to 12,000), polypropylene glycol (M _W 425-8,000), ethyl-propyl cellulose (M _W 800-1,600,000), a thickening agent prepared in solution such as gelatin, pectin; using aqueous or mixed vegetable oil-based dispersion master stock solution is any one selected from the group consisting of glycerin, butanediol, propanediol, pentanediol, hexadiol The mixture of is used as ultrapure water or mixed vegetable oil as diluent. The dispersion master stocks do not emit volatile organic compounds in the manufacturing process and use process, and polythiophene, polypyrrole, polyacene, polyanaline, polyacetylene, fullerene, carbon nanotube, graphene, nano It is an inkjet ink composition to which a wire and a dendrimer can be added.

Ink prepared in the present invention has a surface tension of 20 to 70 dyne / cm; Viscosity is 5.0-300 cPs; And pH 7-14.

Hereinafter, the present invention will be described in detail with reference to the embodiments shown in the accompanying drawings. The examples presented are exemplary and are not intended to limit the scope of the invention.

1 schematically illustrates a process for producing an ink composition according to the present invention.

Referring to Figure 1, the manufacturing process of the ink composition according to the present invention is a dye, pigment phosphorescent (fluorescent) pigment selection step (S11); Preparing a conductive rheological polymer particle (S12); Photocuring dispersion master solution manufacturing step (S13); Milling dispersion step S14; An ink formular step S15; Microfiltration step (S16); And it may include a printing step (S17).

1.Salt-pigment phosphorescent (fluorescent) dye body selection step (S11)

First, a dye or pigment phosphorescent (fluorescent) dye is selected. Dyes and pigments phosphorescent pigments include aqueous based red, green and blue, vegetable oil based optical, white, optical electrodes and insulators. Black for the application. The dye and pigment phosphorescent phosphors according to the present invention include the following materials. Among the following dyes, pigment phosphorescent (fluorescent) pigments and electrically conductive rheology materials, as shown in the provisions of the Oeko-Tex Standard 100 in Europe, a substance with no allergen and carcinogenicity can be used.

blue

Pigment phosphor (fluorescent) body: C.I. Pigment Blue 15; C.I. Pigment Blue 15: 1; C.I. Pigment Blue 15: 2; C.I. Pigment Blue 15: 3; C.I. Pigment Blue 15: 4

Dye phosphor (fluorescent): C.I. Direct Blue 190; C.I. Direct Blue 191; C.I. Direct Blue 192

Natural phosphors: Anthocyanin, Fe-Phtalocyanine, Luminol

Red

Pigment phosphor (fluorescent) body: C.I. Pigment Red 48; C.I. Pigment Red 48: 1; C.I. Pigment Red 48: 2; C.I. Pigment Red 122; C.I. Pigment Violet19

Dye phosphor (fluorescent): C.I. Acid Red 84; C.I. Acid Red 87; C.I. Reactive Red 23

Natural phosphors: Carmine A; Carmine b

green

Pigment phosphor (fluorescent) body: C.I. Pigment Green 7, C.I. Pigment Green 36, Cu-Phtalocyanine,

Phosphor natural: Luciferin

black

Pigment: C.I. Pigment Black 7, direct dye: Poly azo; Poly Phenol, Natural Dyes: Sepia color, Polypyrrole, Graphene, Fullerene, Graphite, Tanono Nanotubes

White

C.I. Pigment White 6 (Rutile type titanium dioxide, C.I.Pigment White 7 (Anatase type titanium dioxide, C.I.Pigment White 31)

Transparency

Zinc Oxide

Transparent electrode

Indium tin oxide

etc

Pigments: CI Pigment Violet 23, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Green 7, CI Pigment Green 36, Phtalocyanine, White Carbon, Lithopone, Aluminum Oxide, Gold, Silver, Chopper, Fe ₂ O ₃ , Lithium, Magnesium, Barium sulfide, CNT (Carbon Nano Tube, SWCNT, MWCNT), Nanowire, Dendrimer, Graphene, Fullerene-C60, 61, 70, 90, PEDOT-POSS / PSS (Poly Thiopene Group), Poly Acetylene, Poly Pyrrole, Poly Phenylene Vinylene, Poly Vinylene Carbazole, Poly Sprazole, Poly acene, Poly aniline, Poly L-glutamate, Iridium, Hafnium.

2. Electromagnetic conductive rheological polymer particle manufacturing step (S12)

The electrically conductive rheological polymers contained 20 to 40 wt% of a polystyrene-acrylate-thiophene-acene-aniline-methylmethacrylate-unsaturated polyester mixture under standard conditions (atmospheric pressure 1ATM, temperature 298.16K); 20 to 40 wt% of a modified silicone fluorinated polyester (such as Do-Corning I2700) mixture of ultrapure water or vegetable oil mixture (20 to 60 wt% of vegetable oil, 20 to 40 wt% of ether, lactam 10 to 20 wt%, lactone 20 ~ 40wt%). Then, 20-40 wt% of the amphoteric (water-soluble and fat-soluble) solvent 2-pyrrolidone and N-methylpyrilidone blend solution (mixing ratio 50:50) in a nitrogen atmosphere, dimethyl sulfoxide and dimethyl acetate blend solution (cosolvent) 50:50) Mixing ratio based on 1Kg) Wurtz Fitting- Ulmann Reaction is achieved by adding 20 to 40 wt% of tetrabutyl alcohol as non-solvent and 2 to 7 wt% of Ag-Au-Pt continuous catalyst. do. Next, when 2-7 wt% of aluminum trioxide dicholoride and Calcium hydrate are added, Ligand Reaction and Ziegler-Natta Reaction simultaneously act to synthesize a conductive rheology polymer. To induce crystallization of the synthesized polymer, it was added dropwise to 1000 ml of azeotrope (isopropyl alcohol / ethyl alcohol volume mixing ratio 20:80) and 1000 ml of 0.01 N HCl and 0.01 N NaOH neutralizing it were added dropwise, and 1 N, an oxidation-reducing agent, was added. 1000 ml of bisphosphocarbonate or disodium sulfonate is added dropwise to form a crystal. Next, styrene, acrylate, methyl methacrylate and polyethyl-propyl by polymerization of heat, light, radiation and microwaves with BPO (benzoic peroxide) 0.1-1 wt% initiator by heat and light under helium atmosphere. 2 or more selected from the group consisting of oxides, spirazole-eosin from Tokyo Chemical Industry, modified silicone / fluorine copolymer from Dow-corning, and polycinnemate (Mw 200,000), a photosensitizer, and inorganic materials (titanium dioxide, silicon dioxide) (Silicone dioxide, aluminum oxide, zinc oxide, at least one selected from the group consisting of indium tin oxide (ITO)) is added in small amounts to synthesize a variety of electromagnetic conductive rheological polymer particles. do. Finally, the active end of the group terminal forms a functional group that is water-soluble or fat-soluble depending on the presence or absence of a hydroxy group. It is manufactured with Degassing using 99.999999999% nitrogen gas from Airproducts during the manufacturing process of electromagnetic conductive rheology polymer.

3. Photocuring  Preparation of Dispersion Master Solution S13 )

Dyes, pigment phosphors or conductive rheology polymers must first be short dispersed to produce a size such that the photocurable inkjet ink can be ejected through the printer nozzle. Dispersing solvents for dispersing dyes, pigment phosphors and electroconductive rheological polymer particles are ultrapure water (Red, Green, Blue, Black pigments) or vegetable oil mixtures (Optical, White, Optical Electronode) (vegetable oil 20) ~ 60wt%, ether 20-40wt%, lactam 10-20wt%, lactone 20-40wt%) is used. The vegetable oil may be used soybean oil, sesame oil, perilla oil or rapeseed oil.

In addition, KOH acid number (Acid number) 100, Amine acid value (Acid number) 300, amphoteric modified silicone-fluorine-based surfactant having a density of 1.42 g / cm 3 was added and stirred sufficiently, and amphoteric photopolythiophenephosphonate-methylmethacrylate-modified unsaturated polyester of Sigma-Aldrich Copolymer or polystyrene phosphonate-methyl methacrylate-modified unsaturated polyester copolymer polymer, modified fluorinated silicone polymer of Dow-corning Co., Ltd. I2700 is added, and modified organic Phenylene Vinylene (PPV) or Tokyo Chemical Industry Sprizole is added to prepare a polymer dispersion suspension (emulsification) solution. Into the prepared polymer dispersion suspension solution, the dye, pigment phosphor (phosphorescent) particles or the above-mentioned electroconductive rheological polymer particles were added to prepare the dispersion master solution having a viscoelasticity by being wetted while slowly stirring. do.

4. milling  Distribution step ( S14 )

The particle size of the dye, pigment phosphor (fluorescent) and the electroconductive rheological polymer particles dispersed (mixed / blended) in the dye, pigment phosphor (phosphorescent) dispersion master solution or dispersion solution of the electroconductive rheological polymer particles grows to the maximum size Is a sub nanoemulation size (0.1 nm) which is not suitable for jetting through an inkjet nozzle. Before going to the ultra fine milling process, milling is performed by pre-milling (rotational speed of 500 to 3000 RPM) and fine milling (rotational speed of 1000 to 8000 RPM) to produce narrow nano-sized dispersions through the aggregation of particles. It must be dispersed to a size suitable to be jetted through the inkjet nozzle. For dispersion, zirconium-silica carbide-hafnium beads of 0.1 to 5 mm are placed in a milling machine to disperse the pigment so that the average particle size of the pigment is 1 to 10 nm for a processing time of 90 minutes at 1 kg. Through this dispersion process, a photocuring ink dispersion master stock solution excellent in dispersion is produced. Beads for dispersing are introduced at about 60 to 90% of the total volume of the machine chamber and the injected zirconium-silica carbide-hafnium beads are rotated at a rate of 4,000 to 24,000 RPM. For this dispersal, ultrafast dry grinding equipment using a zirconium-silica carbide-hafnium bead is used for pilot ultra-high speed dry grinding equipment such as commercially available IKA T-200. do.

5. Ink Formula  step( S15 )

A photoreaction chemical is added to the dispersion master stock solution prepared above. Generally, photoreactive chemicals are added to improve the stability, dispersibility, or binding properties of the ink composition. The added photoreactive chemicals should take into account the improvement of ink properties such as surface tension, viscosity, pH and storage stability and at the same time use materials that are harmless to humans and the environment.

In the present invention, the photoreaction chemicals include pH buffer solutions such as potassium hydroxide, surface tension modifiers, moisturizers, sensitizers, collectors, stabilizers, antifoams, and ultrapure water / vegetable oil mixtures. Ultrapure water is used when the ink composition is water soluble, i.e. contains red, green, blue and black dyes, and vegetable oil mixtures are used for fat soluble, ie optical, white or optical electrodes.

The surface tension modifier is Surfynol CT-211, 221, 231, Dynol 604, 607 Zetasperse 2500, 3100, 3400, 3700, Envirogem AD01, AE01, 02, 03, 360; Tego 270, 280, 500, 505, Disperse 750, 760, an amphoteric surfactant from Degussa; BYK 023, 024, 027, 028, Disper 180, 184, 190, 192, 191, 193, which are amphoteric surfactants from BYK Corporation; Solsperse 27000, 40000, 41000, 41090, 42000, 44000, 46000, 47000, an amphoteric surfactant from Lubirazol; FC-4430, 4432 etc. which are amphoteric surfactants of 3M company can be used preferably.

The moisturizing agent may be a room temperature moisture-curable moisturizing agent such as modified glycerol ethoxy-propoxylate (Sigma-Aldrich, Glycerol ethoxy-prothoxylate), 1,6-hexylene diacrylate. As the photocurable polymer, the prepolymer, and the oligomer, commercially available photocurable polymers, prepolymers, and oligomers may be used, but polyacrylates, polymethylmethacrylates, polyacrylates / polymethylmethacrylate oligomers, and unsaturated polyesters may be used. Prepolymers, polyethylurea prepolymers, polyurethane-acrylate prepolymers, polyethylmethylmethacrylate, hydroxypolyethylmethylmethacrylate, and the like.

As the photocuring monomer, polyacrylate, polymethyl methacrylate, ethyl diacrylate, propyl diacrylate, butyl diacrylate, ethyl methacrylate, propylmethyl methacrylate, butyl methyl methacrylate, iso Propyl acrylamide monomers, hydroxy ethyl methacrylate, hydroxypropyl methyl methacrylate, hydroxybutyl methyl methacrylate and the like can be used.

Finally, the ink composition of the present invention is 14 ~ 28wt% dispersion master solution; 0.1 to 1 wt% pH buffer solution; 1 to 2 wt% of a light cured polymer (including prepolymers and oligomers); 2 to 4 wt% photocuring monomer; 0.1 to 1 wt% surface tension modifier; 0.1 to 1 wt% photoinitiator; 0.1 to 1 wt% thermal initiator; 0.1 to 1 wt% free radical initiator; 0.1 to 1 wt% sensitizer; 0.1 to 1 wt% collecting agent; 0.1 to 1 wt% stabilizer; 0.1 to 1 wt% antifoam; And 1 to 5 wt% humectant.

As the photoinitiator, benzoacetphenone, benzoperoxide, etc. may be used, and azobisbutylnitrile or azobismethylnitrile may be used as the thermal initiator, and 2,2-azobis (2-methylpropion), which is a free radical initiator, may be used. Dihydrochloride (2,2-azobis (2-methylpropion) dihydrodicholoride) may be used.

As the sensitizer, polycinnamate may be used, TINUV 5060, 5061 of BASF (Ciba spe.) May be used as a stabilizer, and hydroperoxide of Sigma-Aldrich may be preferably used as a collecting agent. have.

The ink composition master stock and the photoreaction chemical are blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blending process. In this case, a commercially available variable conditional reaction and storage vessel, which can be controlled by IKA's computer, can be used.

7. Precision filtration step ( S16 )

The prepared ink composition is subjected to a microfiltration process to remove impurities generated or mixed in the manufacturing process and to filter out particles having a predetermined size or more. The filtration process is performed by ultrafiltration (less than 3 μm), fine filtration (less than 500 nm), selective ultra-precision filtration (less than 100 nm) using a Millpore product, and filtered by a reduced pressure (-1 ATM) vacuum pump. Through the filtration process, the ink composition has an overall uniform and stabilized particle size.

8. Printing  step( S17 )

The ink composition of the present invention may accelerate the curing speed of the ink by the photocuring device when printing by configuring the photocuring device in the printing device. In addition, color analysis and matching system is provided for color expression and reproduction, and is automated by parallel processing operation of x86-based or RISC-based processors (32 / 64bit microprocessors such as ARM, Intel, AMD, VIA, IBM, etc.). Ensure a system with excellent output.

2 is a block diagram showing the overall hardware configuration of a three-dimensional printing system according to an embodiment of the present invention. Referring to FIG. 2, a three-dimensional printing system 100 includes a motherboard system including first, second, third, fourth, and fifth motherboard modules 110a, 110b, 110c, 110d, and 110e of the system. And a color profiler 120, a photocuring device 130, a storage device 140, a commercial inkjet printer 150, and a display device 160. Each configuration is interconnected to allow data communication.

The first motherboard module 110a is the main computing system of the system, and FIG. 2 shows a block diagram of the first motherboard module. The first motherboard module 110a is an X86 based 64-bit 8 thread processor that runs an independent operating system. The first motherboard module 110a is capable of parallel processing and displays, prints, inputs, outputs, and stores the same.

The second and third motherboard modules 110b and 110c are auxiliary computing systems of the system, and a block diagram of the second and third motherboard modules is shown in FIG. 3. The second and third motherboard modules 110b and 110c may run an independent operating system as an X86 based 64-bit 4 thread processor. The second and third motherboard modules are capable of parallel processing and are responsible for display, input, output and high speed integer operation.

The fourth motherboard module 110d is a main processing system, and a block diagram of the fourth motherboard module is shown in FIG. 4. The fourth motherboard module 110d is a RISC-based ARM processor capable of parallel processing and is responsible for input, output, and high-speed floating-point arithmetic processing.

The fifth motherboard module 110e is an auxiliary processing system, in which a block diagram of the fifth motherboard module is shown. The fifth motherboard module 110e is a RISC-based Xscale processor capable of high-speed digital operation control and may be driven by a kernel or a shell. The fifth motherboard module handles the input, output and high-speed image and integer and floating point operations of the photocuring control and color management (profiling) control system.

FIG. 3 shows a parallel processing flow of software by the three-dimensional printing system shown in FIG. 2. As shown in FIG. 3, in step S001, the color matching profile information and the photocuring control data are transmitted to the step S002 through the fifth mainboard module to execute the computer parallel dispersion processing operation program, and then to each motherboard module in the step S003. It is distributed and processed. If the operation processed in step S004 and the target value of the operation coincides with the parallel operation using the multi-core by the multi-core of the first motherboard module, if the target value does not match through the step S010 of the second and third motherboard module If the processor is parallelized and processed by a multi-processor, and if the target value is larger than the target value in step S013, the feedback is returned to step S004. If the target value is lower than the target value, the controller moves to the fourth motherboard module (S018) and if the target value is the same in step S013, steps S015 and S016 are performed in sequence, and feedback is sent to step S003 in step S017 to calculate. If the target value is low in step S013, the process moves to steps S018, S019, S020, S021, and S022, and then moves to step S010. This structure is taken as a ring count method of a recursive feedback structure to form software capable of correcting the calculation by the high speed processing.

Flexible electronic components can be manufactured in a simple process using the ink compositions, hardware and software described above and using a three-dimensional photocurable inkjet printer.

Hereinafter, a liquid crystal display will be described as an example among various electronic components. 4A shows a typical liquid crystal display. A liquid crystal display is generally manufactured by a TFT-LCD process, specifically, a polarizing film (phase difference 90 degrees, 180 degrees) 12, 12 'is inserted between glass substrates 11, 11', respectively, and atmospheric pressure ion The surface is treated with a plasma apparatus. Next, the liquid crystal polymer 13 is injected between the substrates, and cell partitions are provided on the substrates to suppress birefringence or reflection of light. Next, after forming the R, G, B (14) in the cell partition wall, a light guide plate plated with silver is installed at the bottom, and a BLU (backlight unit) is installed below it. Reattach the glass substrate to the front to form the LCD.

However, in the case of using the ink composition of the present invention, the ink composition comprising the electroconductive polymer rheology particle ink composition and dye, and pigment fluorescent (phosphorescent) dye prepared above are simultaneously mounted on a printer, and the hardware and software are The liquid crystal display (LCD) of the form shown in FIG. 4B can be manufactured. 4B, after printing the liquid crystal polymer 22 formed of the electromagnetic conductive polymer rheological particle ink composition of the present invention on the organic-inorganic hybrid polyethylene terephthalate film 21, the organic-inorganic hybrid polyethylene terephthalate film ( 21 '), a cell partition wall is formed using a three-dimensional printer, and R, G, and B 23 are continuously formed in the cell partition wall.

The ink composition of the present invention, in addition to the liquid crystal display described above, TFT-LCD (Thin Film Transistor-Liquid Crystal Display), PDP (Plasma Display), SED (Set-off Field Emission Display), FED (Field Emission (Emitting) Display), Organic Limiting Emission Display (OLED), Active Matrix Organic Limiting Emission Display (AMOLED), Inorganic Phosphorus Organic Limiting Emission Display (PLED), Polymer-Organic Limiting Emission Display (Polymer-OLED), Organic Thin Film Transistor- Liquid (OTFT-LCD) Crystal Display), E-paper, Laser Paper, (ultra) High Speed Electrochromic Cell Display, Transmissive Display, etc. Also, two-dimensional, three-dimensional display, transparent transmissive double-sided display, hologram and silicon monocrystalline solar cell, silicon polycrystalline solar cell, polysilicon solar cell, amorphous silicon solar cell, electrically conductive polymer Film sensor, transparent film type solar cell, color light emitting solar cell, gel or polymer type secondary battery, polymer type supercapacitor, polymer electrolyte type fuel cell and chemical sensor manufactured by 3D photocuring digital printer , Biosensors, gel sensors, integrated circuits used in discrete and quantum computers, high integrated circuits, ultra high integrated circuits and electro-electromagnetic shielding materials, antistatic agents, ferroelectrics, ferromagnetic materials, superconductors, polymer thermal conductors, gel thermal conductors, electrical It can be used for conductive high refractive type (flexible) optical fiber.

Hereinafter, the present invention will be described in detail with reference to Preparation Examples and Examples, but the scope of the present invention is not limited or limited by the following description.

Preparation Example 1 Preparation of Electromagnetically Conductive Rheological Photocured Polymer Particles

250 g of amphoteric (water soluble, fat soluble) polystyrene-acrylate-thiophene-acene-aniline-methylmethacrylate-unsaturated polyester mixture of Sigma-Aldrich under nitrogen atmosphere, standard conditions (atmospheric pressure 1 ATM, temperature 298.16 K); 250 g of modified silicone fluorinated silicone-unsaturated polyester mixture of Dow-Corning I2700 was prepared from ultrapure water or vegetable oil mixture (20 to 60 wt% of vegetable oil, 20 to 40 wt% of ether, 10 to 20 wt% of lactam, 20 to 40 wt% of thin film) At the time of formation), 250 g of 2-pyrrolidone and N-methylpyrrolidone blend liquid (based on 1 Kg, mixing ratio 50:50), which is an amphoteric (water-soluble and fat-soluble) solvent, dimethyl sulfoxide and dimethyl acetate blend, which are cosolvents Wurtz Fitting-Ulmann Reaction is performed by adding 200 g of a liquid (50:50 mixing ratio based on 1 Kg), 50 g of tetrabutyl alcohol as a non-cosolvent, and 20 g of Ag-Au-Pt continuous catalyst manufactured by Sigma-Aldrich.

Next, after adding 10 g of Merck aluminum oxide (Aluminum trioxide dichloride) and 20 g of Sigma-Aldrich's calcium hydrate (Calcium hydrate), Ligand Reaction and Ziegler-Natta Reaction were simultaneously performed to synthesize an electroconductive rheology polymer.

In order to induce crystallization of the synthesized polymer, the mixture was added dropwise to 1000 ml of azeotrope (isopropyl alcohol / ethyl alcohol volume mixing ratio 20:80), 1000 ml of 0.01 N HCl and 0.01 N NaOH neutralizing it were added dropwise and oxidized. -1000 ml of 1N bisphosphocarbonate or disodium sulfonate as a reducing agent is added dropwise to form a crystal. Next, 1 g of BPO (benzoic peroxide), an initiator of heat and light, was added in a helium atmosphere, and 250 g of a styrene / acrylate / methyl methacrylate / polyethyl-propyloxide mixture from Merck, a modified silicone / fluoro copolymer of Dow-corning 250 g of polymer, 50 g of spirazole (lipophilic) or eosin (water-soluble) from Tokyo Chemical Industry, an electrochromic substance, and 2 g, 10 g of inorganic material (titanium dioxide, Sigma-Aldrich), a photo-sensitizer, Polycinnemate (Mw 200,000) At least one selected from the group consisting of silicon dioxide, aluminum oxide, zinc oxide or indium tin oxide (ITO) is added to the organic and inorganic layers on the polymer crystals. Polymer particles formed in multiple layers were prepared.

Two or more selected from the group consisting of polythiophene, acene, analin, vinylcarbazole or L-glutamate may be used instead of spirazole or eosin from Tokyo Chemical Industry.

Finally, the electromagnetically conductive rheology polymer synthesized has water solubility or fat solubility depending on the presence or absence of a hydroxyl group at the end of the active group. It is manufactured with Degassing using 99.999999999% nitrogen gas from Airproducts during the manufacturing of conductive rheological polymer particles.

Preparation Example 2 Preparation of Photocuring Dispersion Master Solution Containing Phosphorescent (Fluorescent) Dyestuff

In order to make the dye, the pigment phosphorescent (fluorescent) pigments can be sprayed through the printer nozzle first must be monodisperse. Deionized water (Red, Green, Blue, Black) or vegetable oil mixture (Optical, White, Optical Electrode) (20-60 wt% vegetable oil, ether) as a dispersing solvent to disperse dyes and pigment phosphors 20-40 wt%, lactam 10-20 wt%, lactone 20-40 wt%) is used. In addition, KOH acid number (Acid number) 100, Amine acid value (Acid number 300) 10 g of an amphoteric modified silicone-fluorine-based surfactant having a density of 1.42 g / cm 3 is added to 300 g of the ultrapure water or vegetable oil and then sufficiently stirred. Next, 300 g of amphoteric photopolythiophenephosphonate (polystyrene phosphate) -methyl methacrylate-modified unsaturated polyester copolymer polymer of Sigma-Aldrich, and 100 g of modified fluorinated silicone polymer of Dow-corning company I2700 were added, A polymer dispersion suspension (emulsification) solution is prepared by adding 100 g of modified polyphenylene vinylene (PPV), Merck's organic light emitting material, and 200 g of sprazole or eosine (Tokyo Chemical Industry). 300 g of the dye and the pigment phosphorescent (fluorescent) dye were added to the polymer dispersion suspension solution so that wetting was performed while slowly stirring to prepare a dispersion master solution having viscoelasticity. During the preparation, it was prepared with Degassing using 99.999999999% nitrogen gas from Airproducts.

Preparation Example 3 Preparation Example of Photocuring Dispersion Master Solution Containing Electromagnetic Conductive Rheological Polymer Particles

300 g of the conductive rheological polymer particles prepared in Preparation Example 1 were added instead of the dye and the pigment phosphor pigment in Preparation Example 2, and a photocured dispersion master solution was prepared in the same manner as in Preparation Example 2.

Example 1 Preparation of Blue Dye, Pigment Phosphorescent (Fluorescent) Photocurable Ink Composition

In Preparation Example 2, a blue master dispersion stock solution was prepared using a blue dye and a pigment phosphor dye as dyes and pigment phosphor pigments. A blue light curing ink composition was prepared by adding the prepared blue master dispersion stock solution and the following photo curing reaction chemicals.

150 g of blue master dispersion stock solution; 767 g of ultra pure water;

20 g of hydroxy polyethyl methyl methacrylate (photocured polymer); 40 g of hydroxy ethyl methyl methacrylate (photocured monomer); 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 1 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The resulting ink had a surface tension of 25 dyne / cm; Viscosity 13.9 cPs; And pH 9.3. The prepared ink was injected into a cartridge and subjected to a 30 m output test on output devices such as the Stylus Pro 7900 manufactured by Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 manufactured by Canon. In the test procedure, a polyethylene terephthalate film was used for printing. No ejection of the nozzle occurred and the durability and sharpness of the printed phosphor ink were good in the test.

Example  2-red dyes, pigments Phosphor  Photocuring ink manufacturing

In Preparation Example 2, a blue master dispersion stock solution was prepared using red dye and pigment phosphor pigment as dyes and pigment phosphor pigments. A blue photocurable ink composition was prepared by adding the prepared blue master dispersion stock solution and the following photocuring reaction chemicals.

160 g red master dispersion stock solution; 757 g of ultra pure water; 20 g of hydroxy polyethylmethylmethacrylate (photocured polymer); 40 g of hydroxy propylmethyl methacrylate (photocuring monomer); 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The inks obtained as a result of the prepared ink composition had a surface tension of 26 dyne / cm; Viscosity 13.6 cPs; And pH 9.1. Filtering was conducted in the same manner as in Example 1 using a test such as a Stylus Pro 7900 manufactured by Epson, a Hewlett Packard Designer jet z3200, and a Canon IPF 8000 manufactured by Canon. In the same manner as in Example 1, printing was performed using a polyethylene terephthalate film. No printout of the nozzle resulted in the printout, and the durability and sharpness of the printed phosphor ink were good in the test.

Example  3- Green Dye, Pigment Phosphor  Photocuring ink manufacturing

In Preparation Example 2, a green master dispersion stock solution was prepared using green dye and pigment phosphor dye as dyes and pigment phosphor pigments. The green photocurable ink composition was prepared by adding the prepared green master dispersion stock solution and the following photocuring reaction chemicals.

150 g of a green master dispersion stock solution; 767 g of ultra pure water; 20 g of hydroxy polyethylmethylmethacrylate; 40 g of hydroxyethylmethylmethacrylate; 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The final ink produced had a surface tension of 27 dyne / cm; Viscosity 13.4 cPs; And pH 8.8. A 30 m power test was performed on output equipment such as the Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. The printing was done using a polyethylene terephthalate film in the course of the test.

Example  4- Insulation  And electromagnetic For shielding materials  Black dye, pigment photocuring ink manufacturing

In Preparation Example 2, the assay master dispersion stock solution was prepared using black dye, pigment phosphor pigment or polypyrrole, graphene, fullerene, graphite, or tannonanotube in place of the dye and pigment phosphor pigment. A blue light curing ink composition was prepared by adding the prepared assay master dispersion stock solution and the following photo curing reaction chemicals.

180 g of the assay dispersion stock solution; 737 g of ultrapure water; 20 g of hydroxy polyethylmethylmethacrylate; 40 g of hydroxyethylmethylmethacrylate; 10 g of 1,6-hexylenediacrylate (humidifying agent); 1 g of Potassium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The resulting ink had a surface tension of 26 dyne / cm; Viscosity 14.2 cPs; And pH 10.0. A 30 m power test was performed on output equipment such as the Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. The printing was done using a polyethylene terephthalate film in the course of the test. No ejection of the nozzle occurred and the durability and sharpness of the printed ink were good in the test.

Example  5-display protective clear dye, pigment zinc oxide ( Zinc oxide Based) photocurable ink manufacturing

In Preparation Example 2, a transparent master dispersion stock solution was prepared using zinc oxide instead of a dye and a pigment phosphor pigment. A transparent photocurable ink composition was prepared by adding the prepared transparent master dispersion stock solution and the following photocuring reaction chemicals.

150 g of a transparent master dispersion stock solution; 767 g of vegetable oil mixture (40 wt% of vegetable oil, 30 wt% of diethylene monobutyl ether, 10 wt% of 2-pyrrolidone, and 20 wt% of gamma butyrolactone); 20 g of polypropylmethylmethacrylate; 40 g of ethylpropyl methacrylate; 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The final ink produced had a surface tension of 27 dyne / cm; Viscosity 9.9 cp; And pH 9.5. Output tests were conducted using equipment such as Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. In the same manner as in Example 1 was printed using a polyethylene terephthalate film. No ejection of the nozzle occurred and the durability and sharpness of the printed ink were good in the test.

Example  6-General White ( Titanium Dioxide Based) dyes, pigment photocuring ink manufacturing

In Preparation Example 2, a white master dispersion stock solution was prepared using titanium dioxide (Titanium Dioxide) instead of the dye and the pigment phosphor pigment. A white photocurable ink composition was prepared by adding the prepared white master dispersion stock solution and the following photocuring reaction chemicals.

240 g of a white dispersion master stock solution; 677 g of vegetable oil mixture (40 wt% vegetable oil, 30 wt% diethylene monobutyl ether, 10 wt% 2-pyrrolidone, 20 wt% gamma butyrolactone); 20 g of polypropylmethylmethacrylate; 40 g of ethylpropyl methacrylate; 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The final ink produced had a surface tension of 27 dyne / cm; Viscosity 14.9 cp; And pH 9.7. Output tests were conducted using equipment such as Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. In Example 1 and the test procedure, a polyethylene terephthalate film was used for printing. No ejection of the nozzle occurred and the durability and sharpness of the printed ink were good in the test.

Example  7-liquid crystal ( Liquid Crystal Electromagnetic conductivity Rheology  Polymer ( Poly Ethyl  Dioctyl Thiopene Based) particle photocurable ink manufacturing

A conductive polymer photocurable ink composition was prepared by adding the conductive rheological polymer master dispersion solution prepared in Preparation Example 3 and the following photocuring reaction chemicals.

Conductive rheological polymer master dispersion 220g; 697 g of vegetable oil mixture (40 wt% vegetable oil, 30 wt% triethylene monobutyl ether, 10 wt% N-methylpyrrolidone, 20 wt% valerolactone); 20 g of polypropylmethylmethacrylate; 40 g of ethylpropyl methacrylate; 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The inks obtained as a result of the prepared ink composition had a surface tension of 27 dyne / cm; Viscosity 13.9 cp; And pH 10.1. Output tests were conducted using equipment such as Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. In the same manner as in Example 1, printing was performed using a polyethylene terephthalate film. No ejection of the nozzle occurred and the durability and sharpness of the printed ink were good in the test.

Example 8 Transparent Electrode (Indium Tin Oxide-Based) Photocurable Ink Composition

In Preparation Example 2, a white master dispersion stock solution was prepared using ITO (Indium Tin Oxide) having a particle size of 6 nm instead of a dye and a pigment phosphor pigment. A transparent electrode photocurable ink composition was prepared by adding the prepared transparent electrode master dispersion stock solution and the following photo curing reaction chemicals.

280 g of a transparent electrode master dispersion stock solution; 637 g of vegetable oil mixture (40 wt% vegetable oil, 30 wt% triethylene monobutyl ether, 10 wt% N-methylpyrrolidone, 20 wt% valerolactone); 20 g of polypropylmethylmethacrylate; 40 g of ethylpropyl methacrylate; 10 g of 1,6-hexylenediacrylate (moisturizer); 1 g of Potassisium hydroxide (pH buffer solution); 1 g of Dioctyl sulfosucinate, disodium salt (defoamer); 1 g Dynol 604 (surface tension modifier); 1 g of Benzo-aceto-phenone or Benzo peroxide (photoinitiator); 1 g of 2,2-Azobis (2-methylpropion) dihydrodicholoride (free radical initiator); 5 g of Poly cinnamate (sensitizer); 1 g of Hydro peroxide; 1 g TINUVIN 5060 (stabilizer).

The ink composition is blended in a mechanical stirrer and prepared with Degassing using 99.999999999% nitrogen and helium gas from Airproducts during the blend. The prepared ink composition was filtered using a member filter. The inks obtained as a result of the prepared ink composition had a surface tension of 28 dyne / cm; Viscosity 15.9 cp; And pH 9.9. Output tests were conducted using equipment such as Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. In the same manner as in Example 1, printing was performed using a polyethylene terephthalate film. No ejection of the nozzle occurred and the durability and sharpness of the printed ink were good in the test.

Example 9

The ink composition of Example 6 was printed and photocured on Sigma-Aldrich's conductive PET film (product number: 700177) using equipment such as Stylus Pro 7900, Hewlett Packard Designer jet z3200, Canon's Canon IPF 8000, etc., of Epson. Next, the electromagnetic conductive rheological polymer ink of Example 7 was printed and photocured. After placing the conductive PET film (Product No .: 700177) of Sigma-Aldrich on it, the blue and red green inks of Examples 1 to 3 and the ink of Example 4 to make cell partition walls were simultaneously printed and photocured. Next, a flexible display was completed by connecting metal conductive wires using a Roll to Roll (R2R: Screen Printing) method.

Example 10

The ink composition of Example 6 is printed and photocured on a Sigma-Aldrich Co., Ltd. conductive PET film (product number: 700177) using equipment such as Stylus Pro 7900, Hewlett Packard Designer jet z3200, Canon Canon IPF 8000, etc. of Epson. Next, the electromagnetic conductive rheological polymer ink of Example 7 is printed and photocured. After placing the conductive PET film (Product No .: 700177) of Sigma-Aldrich on it, the blue and red green inks of Examples 1 to 3 and the ink of Example 4 to make cell partition walls are simultaneously printed and photocured. Next, Example 8 was printed and photocured to complete the flexible display.

Example 11

The ink composition of Example 6 is printed and photocured on a Sigma-Aldrich Co., Ltd. conductive PET film (product number: 700177) using equipment such as Stylus Pro 7900, Hewlett Packard Designer jet z3200, Canon Canon IPF 8000, etc. of Epson. Next, the electromagnetic conductive rheological polymer ink of Example 7 is printed and photocured. After placing the conductive PET film (Product No .: 700177) of Sigma-Aldrich on it, the blue and red green inks of Examples 1 to 3 and the ink of Example 4 to make cell partition walls are simultaneously printed and photocured. Next, Example 8 was printed and photocured, and Example 5 was printed and photocured to complete a flexible display.

The conventional display has a thickness of 5 mm, but the display manufactured in Example 11 has a thickness of 100 μm. In addition, the power of the conventional display is 50 ~ 60Hz, DC 19v of AC 220v and 60w when the screen size is 22.1 inches, but the display manufactured in Example 11 consumes 6w at 5v DC at the same screen size. Only the same image can be expressed closer to natural colors. FIG. 5 shows the color range of the display (red), NTSC (purple), Adobe RGB (yellow), and commercially available TFT LCD (green) manufactured in Example 11. FIG. It can be seen that the color range of the display (red, green, blue) manufactured in Example 11 is close to the Adobe RGB or NTSC color range, which means that the color range is wide, and the color efficiency and reproduction are excellent.

Comparative Example 1

200g of CI Pigment Blue 15: 3, CI Pigment Red 122, CI Pigment Green 7, and CI Pigment Black 7 based on the P22 standard used for LCD and OLED, 200g each, and stirred sufficiently After the dispersion, a dispersion stock solution having an average particle size of about 20 nm was prepared. The following reaction chemicals were added to the obtained dispersion stock solution to prepare a UV curable ink constituent for petroleum dilution electronic screen printing.

12 wt% of pigment dispersion stock solution; Aryl glycol 42 wt%; Dendrimer 7 5 wt%; Polyphenylenevinyl 8 wt%; Irgacure 819 5 wt%; and 28 wt% N-vinylflodene.

The prepared petroleum dilution UV curable inks were tested on output devices such as Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200, and Canon IPF 8000 from Canon. During the test process, the nozzle was ejected on the polyethylene terephthalate film, and ink bleeding occurred. In addition, a small amount of methane and carbon dioxide gas was generated during the curing process to increase the air pollution of the indoor space. Later, in the washing step, the durability and sharpness of Examples 9, 10 and 11 were much lower.

The invention has been described in detail by presenting examples. The presented embodiments are illustrative and can be made by those skilled in the art to various modifications and modifications to the disclosed embodiments without departing from the spirit of the invention. The invention is not limited by the invention as such variations and modifications are limited only by the claims appended hereto.

Claims (7)

Preparing a mixture A by mixing a polystyrene-acrylate copolymer, thiophene, acene, aniline, methylmethacrylate and an unsaturated polyester;
Preparing a mixture B by mixing modified silicone fluoride and unsaturated polyester;
Adding the mixture A and the mixture B to ultrapure water or a vegetable oil mixture, and then polymerizing in the presence of a solvent and a catalyst to prepare a polymer;
Synthesizing a conductive polymer by adding aluminum oxide and calcium hydrate to the polymer;
Preparing a crystallized conductive polymer by dropping the conductive polymer into an azeotrope in which isopropyl alcohol and ethyl alcohol are mixed at a volume ratio of 20:80 (volume ratio);
In the crystallized conductive polymer, an initiator, a photosensitizer, a mixture of two or more selected from the group consisting of styrene / acrylate / methylmethacrylate / polyethyl-propyloxide, a modified silicone / fluoro copolymer, an electrochromic material and an inorganic substance Adding to prepare an electromagnetic conductive polymer particle;
Preparing a photocured dispersion master solution A containing the electromagnetic conductive polymer particles;
Milling and dispersing the photocured dispersion master solution A; And
Mixing a polymer, a photocuring monomer, a photoinitiator, and a free radical initiator with the dispersed photocurable dispersion master solution A, and performing fine filtration; And the electrochromic material is a mixture of two or more selected from the group consisting of spirazole / eosin / polythiophene / acene / aniline. delete delete The method according to claim 1,
Preparing a mixture C by mixing the photocurable dispersion master solution with an ultrapure water or vegetable oil mixture and a surfactant;
To the mixture C, a polythiophene phosphonate-methyl methacrylate-modified unsaturated polyester copolymer polymer or a polystyrene phosphonate-methyl methacrylate-modified unsaturated polyester copolymer polymer, a modified fluorinated silicone polymer and an electromagnetic conductive polymer are added To prepare a polymer dispersion solution; And
The method of manufacturing a photocurable ink composition for an electronic material or an electrical material, characterized in that it is prepared by the method comprising the steps of adding and dispersing electromagnetic conductive polymer particles to the polymer dispersion solution while stirring. The method of claim 1, wherein the photocurable ink composition for an electronic or electrical material is 14 to 28% by weight of the photocurable dispersion master solution A, 60 to 80% by weight of water or vegetable oil mixture, 0.1 to 1 pH of the total composition % By weight, 3 to 6% by weight of the photocuring monomer, 0.1 to 1% by weight of the surface tension regulator, 0.1 to 1% by weight at least one selected from the group consisting of photoinitiator, thermal initiator and free radical initiator, 0.1 to 5% by weight sensitizer , 0.1-1% by weight collecting agent, 0.1-1% by weight stabilizer, 0.1-1% by weight of antifoaming agent and 0.5-1% by weight of moisturizing agent. An electronic component or an electrical component manufactured by printing with a three-dimensional photocurable digital printer using the photocurable ink composition for the electronic material or electrical material prepared in claim 1. The electrical or electronic component of claim 6, wherein the electronic component or the electrical component is a liquid crystal display, an organic or inorganic light emitting display, a plasma display, an electrochromic display, an electroluminescent display, a solar cell, or a biosensor.

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