KR20180003881A - Composite materials for 3d printing, and method for manufacturing electronic parts using the same - Google Patents

Abstract

The present invention relates to a composite materials for three-dimensional printing, and to a method for manufacturing electronic parts using the same, and to a method for forming a conductive structure by selective reduction, in which a metal precursor is ionized to polymeric binders forming hydrogen bonds in a solution, processed into a metal organic complex polymer complex filament which forms an organic ion bond in a polymer binder and is three-dimensionally printed to form a conductive structure by selective reduction.

Description

TECHNICAL FIELD [0001] The present invention relates to a composite material for 3D printing, and a manufacturing method of an electronic part using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a composite material for 3D printing and a method of manufacturing an electronic part using the composite material. More particularly, the present invention relates to a composite material for producing a conductive filament for FDM (Fused Deposition Modeling) 3D printing using extrusion lamination, The present invention relates to a method of manufacturing an electronic component.

3D printing technology is called the third industrial revolution that can fundamentally change the existing factory and market-based mass production distribution system, and its applicable range is gradually expanding. 3D printing related technology is completed by combining material technology, 3D modeling technology, and 3D printing technology that accurately stacks 3D objects and creates 3D objects. Especially, it is necessary to develop various materials that are limited in selecting materials.

Development of electronics, information and communication technologies, miniaturization, highly integrated electronic circuit patterns and various electronic components have been demanded, and the production of electronic parts using 3D printers is also getting attention. Currently, there are ABS, PLA, HIPS, POM, wood and nylon filament types for FDM which are commercialized. PLA and ABS resin are used for more than 80% of the used amount. ABS is widely used because it has various colors, excellent adhesiveness and uniform melting point, but it can not achieve the conductive properties required in industry in recent years.

Conductive filament materials for conventional 3D printers are manufactured by extrusion processing by blending conductive fillers such as carbon black, carbon nanotubes, carbon nanofibers, and graphite with thermoplastic polymers. These conventional conductive filaments must be mixed with 50 to 80% by weight filler in order to exhibit conductivity. Metal or carbon fillers have a disadvantage in that the complexes using the metal or carbon fillers are superimposed on each other by van der Waals force having relatively weak force, so that delamination can easily occur in a printed product having poor fluidity. Also, since the printing nozzles frequently clog due to the presence of excessive filler, the printing material may not be distributed or contamination may occur due to inaccurate distribution. Therefore, there is a limitation that is difficult to form for forming electronic parts having fine three- have.

Accordingly, the present invention is intended to solve problems such as difficulty in dispersion, necessity of addition of a high concentration of filler, and post-treatment instability which are generated in the production of conductive filament for 3D printer using existing metal particles or carbon filler, One of the objects of the present invention is to provide a conductive filament which can be applied to a 3D printer of FDM type by extruding with a small extruder and a method of manufacturing an electronic part using the conductive filament.

Another object of the present invention is to provide a composite material for 3D printing capable of manufacturing an electronic part having a complicated shape in which a conductive pattern is formed, and a method of manufacturing an electronic part showing conductivity using the same.

It is another object of the present invention to provide a 3D structure having a metal surface by a chemical reduction reaction after a 3D structure is formed without clogging the nozzle during printing due to the presence of a conductive material as a metal organic complex during 3D printing. And a method of manufacturing the electronic component.

One aspect of the present invention for achieving the above object is to provide a cage-effect-imparting cage-containing polymer composition comprising a carboxylic acid-based, sulfonic acid-, or phosphonic acid-based polybasic base providing a cage effect, a carboxylic acid- The present invention relates to a composite material for 3D printing comprising a hydrogen-bonding polymer and a metal precursor which form a two-component polymer composite by hydrogen bonding with a polyvalent base.

The metal precursor may be selected from the group consisting of gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, cobalt, lithium, zirconium, lead, tin, titanium, molybdenum, tungsten, tantalum, vanadium, Niobium, aluminum, and magnesium.

The bicomponent polymer complex may be a hydrogen bonding interpolymer complex between a polyacid and a polybase or a low molecular weight compound. The polyacids are selected from the group consisting of polyacrylic acid (PAA), polymethacrylic acid (PMMA), 1,3-adamantanedioic acid, 1,3-adamantanedicarboxylic acid, azelaic acid, benzylmalonic acid, Dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, bis (carboxymethyl) trithiocarbonate, 2-bromoterephthalic acid, 1,2,3,4- Carboxylic acid, 5-tert-butylisophthalic acid, butylmalonic acid, chlorosuccinic acid, 1,1-cyclohexanediacetic acid, trans-1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid There may be mentioned acid, 1,3,5-cyclohexanetricarboxylic acid, cyclohexylsuccinic acid, trans-DL-1,2-cyclopentanedicarboxylic acid, dibromomaleic acid, 2,3-dibromosuccinic acid, Dibromosuccinic acid, 4,5-dichlorophthalic acid, diethylmalonic acid, 3,4-dihydroxyhydrocinnamic acid, 2,5-dihydroxyterephthalic acid, docosanedioic acid, ethylmalonic acid, 3-fluorophthalic acid, hexadecanedioic acid, 2,2 Naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2-methoxyisophthalic acid, 4-methylphthalic acid, 6-methylpyridine-2,3-dicarboxylic acid, 3-phenylglutaric acid, phenylmalonic acid, 3-phenylglutaric acid, 4-phenylglutaric acid, 3-phenylglutaric acid, , 5-sulfoisophthalic acid monolithium salt, 4,4'-sulfonyldibenzoic acid, 4-sulfophthalic acid, sulfosuccinic acid, terephthalic acid, 1,4,8,11-tetraazacyclotetradecane- Tetraacetic acid tetrahydrochloride hydrate, tetrafluoroisophthalic acid, tetrafluorophthalic acid, 3-thiophenemalonic acid, 1,2,3-triazole-4,5-dicarboxylic acid, cis, cis-1 , 3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid, undecanedioic acid, polystyrenesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, sulfoacetic acid ethanesulfonic acid, 3- Hi 1-sulfonic acid, DL-homocysteic acid, 3- (amidino (methoxycarbonyl) aminosalicylic acid, Thio) -1-propanesulfonic acid, 2- (trimethylsilyl) ethanesulfonic acid sodium salt, tridecapryluorohexane-1-sulfonic acid potassium salt, hydroxyquinone sulfonic acid potassium salt, benzenesulfonic acid, 1-naphthalenesulfonic acid, Examples of the polybasic acid group may be selected from the group consisting of sulfonic acid, phosphoric acid, triphosphoric acid, polyphosphoric acid, polyphosphate, cyclic trimethylphosphate, adenosine diphosphate, adenosine triphosphate, , Polyethylene oxide, polyacrylamide, poly (N-vinylpyrrolidone), polyurethane, polyurea.

The composite material of the present invention comprises 3 to 30% by weight of the metal precursor based on 100% by weight of the total composite material.

Another aspect of the present invention for achieving the above object is to provide a cage-effect-imparting cage-containing polymer composition comprising a carboxylic acid type, a sulfonic acid type, or a phosphonic acid type polyvalent base, a carboxylic acid type, a sulfonic acid type, Wherein the conductive material is formed by 3D printing using a composite material comprising a hydrogen-bonding polymer and a metal precursor forming a two-component polymer complex by hydrogen bonding with a base, and reducing the obtained printing material to form a conductive electronic part And a method for producing the same.

The method of the present invention can be used in combination with a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polybasic base which provides a cage effect, a carboxylic acid-based, sulfonic acid- Preparing a film by blending the hydrogen-bonding polymer and the metal precursor forming the two-component polymer composite;

Preparing a composite material for 3D printing by mixing the polymer with a plasticizer and extruding it into a filament, after finely pulverizing the film and then imparting flexibility thereto;

Fabricating the composite material for 3D printing as an electronic component by 3D printing; And

And reducing the electronic component to form a conductive electronic component.

Another aspect of the present invention relates to a 3D-shaped electronic component including a conductive pattern, which is manufactured by the manufacturing method of the present invention.

According to the composite material of the present invention, since the metal precursor improves the dispersibility and thermal stability of the metal precursor, which is a filler for imparting conductivity by constituting an ion complex with a polybasic base providing a cage effect, It is possible to maximize the electrical conductivity while improving the mechanical properties of the filament to be produced at the same time and to maintain the flexibility of the polymer binder while maintaining the excellent conductivity and to improve the quality of post-processing of the 3D stereoscopic shape.

According to the present invention, in 3D printing, a conductive filler exists as a metal organic complex so that a 3D-shaped electronic component is molded without clogging the nozzle, and then a metal surface is formed by chemical reduction in a post- A conductive pattern can be easily formed.

In addition, according to the present invention, it is possible to form a conductive pattern by chemical reduction after 3D printing, so that it is easy to form a conductive pattern in any position or curved shape regardless of the form of an electronic part, Is expected to do. Further, by using a composite material for 3D printing, a conductive pattern can be formed on a flexible electronic part, and the application field thereof is expected to be very wide.

Therefore, the 3D stereoscopic electronic component manufactured according to the present invention can be applied to electrodes, transistor pins, connection jacks, various flexible electronic devices, and the like, and can be applied to mobile phone antennas and motor driving circuits, sensor circuits, It can be applied to a wide range of fields, such as medical portable devices, and is expected to contribute greatly to industrial development.

1 shows an example of a 3D printer of the FDM type.
2 shows a process for producing a composite material for 3D printing according to an embodiment of the present invention.
FIG. 3 is a graph showing a result of improving thermal stability at a high temperature in a 3D printing process of a metal precursor by a cage effect in the present invention.
4 is a flow chart for explaining the manufacturing process of the composite material for 3D printing according to the present invention.
5 shows an FE-SEM photograph of a filament for 3D printing formed in an embodiment of the present invention.
Figure 6 is a photograph of a reduced conductive pattern after 3D printing in an embodiment of the present invention.
7 is a photograph showing a result of a light emission test using a circuit manufactured according to the method of manufacturing an electronic part according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.

One embodiment of the present invention relates to a method for producing a cage composition, which comprises a carboxylic acid-based, sulfonic acid-, or phosphonic acid-based polyvalent base providing a cage effect, a carboxylic acid-based, And a metal precursor that forms a two-dimensional polymer complex by hydrogen bonding, and a metal precursor.

The bicomponent polymer composite may be a hydrogen bonding interpolymer complex. The bicomponent polymer composite may protect the polymer composite material from thermal decomposition at a higher processing temperature than a single polymer material that does not form a composite . For example, a hydrogen-bonded polymer composite of polylactic acid and polyacrylic acid can be thermally and chemically protected as compared with polylactic acid alone or polyacrylic acid alone. The hydrogen-bonding polymer which forms the two-component polymer composite by hydrogen bonding with carboxylic acid, sulfonic acid, or phosphonic acid based polyvalent base which provides the cage effect forms a hydrogen bond due to the substitution reaction of the carboxyl group when ionized in the solution . A hydrogen bond can be defined as the attraction between two groups of molecules that contain at least one hydrogen atom and contribute to the interaction. Hydrogen bonds are located between two dyes (A, B) and can induce self-assembly to determine the crystal arrangement of many organic or organic molecules.

  In the above formula, A is a polyvalent acid and B is a polyvalent base.

When the metal precursor is present in solution in the composite material of the present invention, the interaction of the solvent and the solute causes a " cage effect ". The two molecules that are once spatially bound are separated by diffusion The two molecules in the reactor are arranged in a fairly regular arrangement by repeating a number of collisions until they reach the bottom of the reactor. By using this phenomenon, a metal organic complex , MOC). In the ionic reaction of the solute, the main factors of the cage effect are the permittivity of the solvent, the ionic strength of the solution, the hydrogen ion concentration, and also serves to change the activity coefficient.

In general, during FDM 3D printing, the metal precursor compound is likely to undergo thermal reduction and decomposition because it proceeds by melt extrusion at a temperature of about 160 ° C to 280 ° C. In the present invention, A sulfonic acid-based or phosphonic acid-based polybasic base which forms a covalent bond with a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polybasic base which provides the above-mentioned cage effect. Such a bicomponent polymer complex can form a metal organic complex having a cage effect due to ionization of a solute in a solvent, thereby protecting the metal precursor from thermal reduction. FIG. 3 is a graph for explaining that the metal precursor is protected in the filament manufacturing process by the cage effect in the present invention. FIG. 5 is a graph showing the results of TGA analysis of a general metal precursor and a filament composite material of the present invention while raising the temperature. FIG. Referring to FIG. 3, it can be confirmed that the composite material having the cage effect of the present invention significantly suppresses thermal reduction and decomposition even at a high temperature of 300 ° C. or higher. Therefore, the cage effect protects the metal precursor from being reduced to metal by thermal reduction during the high temperature extrusion process.

Based polymer having a carboxylic acid group, a sulfonic acid group, or a phosphonic acid group based on a carboxyl group, a sulfonic acid group, or a phosphonic acid group-containing polyvalent base which provides a cage effect in solution and a cage- The metal organic complex conductive material formed by ionizing the hydrogen-bonded polymer and the metal precursor is made into a pellet shape. In order to apply this pellet type material to a FDM type 3D printer which is easy to produce at low cost, extrusion processing step is required to be made into a filament material. In this case, since the metal organic complex conductive material has strong intermolecular force, it is a polyatomic complex, which lowers the flexibility and flexibility of the material. Therefore, in order to uniformly extrude the filament with a standard diameter of 1.75 mm for the FDM type 3D printer, A third polymer or plasticizer which is similar to the extrusion temperature (160 to 180 DEG C) of the extruder and can increase flowability and processability can be added. Such a polymer additive or plasticizer can improve the flowability of the composite material and consequently improve the flexibility and mechanical strength of the filament. In the present invention, a polyvalent base giving a cage effect, a polymer having a hydrogen bond, and a material imparting flexibility are different materials.

The conductive filament using the metal organic complex of the present invention forms a metal organic complex in order to impart conductivity to the first polymer combination having selective hydrogen bonding to form a polymer complex for thermal stability and 3D printing, A second material forming a cage effect for not being reduced to a metal by thermal reduction, and a third material for imparting the flexibility of the filament if necessary. The conductive metal organic complex filament formed by the composite material of the present invention forms a stable one-dimensional, two-dimensional or three-dimensional metal complex after high-temperature 3D printing in the FDM system, and then selectively metal- A conductive network can be formed to form a conductive network.

In the present invention, the polymer having a hydrogen bond may be selected from the group consisting of PAA (poly (acrylic acid)), PLA (polylactic acid), polyamide, aramid, polyester, polyvinyl, polyacrylonitrile, cellulose, polyurethane, UPy ureidopyrimidione, DEAP (deazapterin), ureidoguano-sine, collagen, silk, PVPh (poly (4-vinylphenol), PVAL (polyvinyl alcohol), PVP PEG (polyethylene glycol), PEO (poly (ethylene oxide)), PHB (poly (3-hydroxybutyrate) ), PPG (polypropylene glycol), PTMG (polytetramethylene glycol), PCL (poly (3-caprolactone)), TDP (4,4'-thiodiphenol), PMVT Poly (styrene sulfonate)), PAMP (poly (vinylidene fluoride)), PAPP (poly (vinylidene chloride) Acryloyl-N'-methyl)), P2VPy (poly (2-vinylpyridine (N, N-dimethylacrylamide)), PVP (poly (N-vinyl-2-pyrrolidone)), PMVAc Poly (2-ethyl-2-oxazoline), DMBVPh (poly (2,3-dimethylbutadiene stat-4-vinylphenol)), PAMAs (poly (N-alkylmethacrylate) S, PDIS (Ethylene / vinyl acetate), EVAL (ethylene / vinyl alcohol), DDA (dodecanedioic acid) DMBAMA (2,3) (Styrene-B-2-ethyl-2-oxazoline), P (VA-CO-VAL) (poly (vinyl acetate- co-vinyl alcohol) PAPP (poly (N-acryloyl-N'-phenylpiperazine)), PAS (poly (p-acetoxystyrene)), PBA (poly (butyl acrylate) (Poly (n-butyl methacrylate)), PCHMA (poly (cyclohexyl methacrylate)), PDLLA (poly (D, L-lactide) ), PDMA (poly (N, N-dimethylacrylamide)), PEAA (poly (N, N-dimethylacrylamide)), PEMA ), PMMA (polymethyl methacrylate), PMMAA (poly (methyl methacrylate-co-acrylic acid)), POM (polyoxymethylene), PP (polypropylene), PPO (poly (2,6- Poly (vinyl acetate)), PVDF (styrene-co-acrylic acid), PSAA (poly (styrene-co-acrylic acid) (Poly (vinylidene fluoride)), PVME (poly (vinyl methyl ether)), PVP (poly (N-vinyl-2-pyrrolidone) (Styrene / vinylpyridine), SBA (suberic acid), SCA (succinic acid) STVPh (styrene / vinylphenol), SVBDEP (styrene / 4-vinylbenzenephosphonic acid diethyl ester), isotactic VBDEP (4-vinylbenzenephosphonic acid Ethyl ester) VPH (4-vinyl phenol), aPHB (atactic poly (3-hydroxy)) , iPMMA (isotactic polymethyl methacrylate), iPHB (isotactic poly (3-hydroxy)), iPMMA (isotactic polymethyl methacrylate), sPHB (syndiotactic poly , sPMMA (syndiotactic polymethylmethacrylate), and the like.

In the present invention, the metal precursor may be at least one selected from gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, cobalt, lithium, zirconium, lead, tin, titanium, molybdenum, tungsten, tantalum, , Chromium, niobium, aluminum, and magnesium.

Non-limiting examples of such metal precursors include silver acetate, silver acetyl acetonate, silver benzoate, silver bis (trifluoromethanesulfonyl) imide, silver bromate, silver bromide, silver carbonate, silver chlorate, silver (I) chloride, silver chromate, silver citrate hydrate, silver-copper alloy, silver cyanate, silver cyanide, silver cyclohexane butyrate, silver diethyldithiocarbamate, silver- Silver (II) fluoride, silver heptafluorobutyrate, silver hexafluoroantimonate (V), silver hexafluoroarsenate (V), silver hexafluorophosphate, silver iodide, silver rock Tate, silver methanesulfonate, silver molybdate, silver nitrate, silver oxide, silver (I) oxide, (I) sulphodiazine, silver (I) sulphonate, silver (I) sulphonate, silver (I) sulphonate, (I) telluride, silver tetrafluoroborate, silver thiocyanate, silver-tin alloy, silver p-toluenesulfonate, silver trifluoroacetate, silver trifluoromethanesulfonate, (III) bromide, gold (I) chloride, gold (III) chloride hydrate, gold (III) chloride hydrate, gold (III) chloride, gold (I) cyanide, gold Iodide, Gold (III) Oxide Hydrate, Gold (I) Sulfide, Gold (III) Sulfide, Copper, Copper (I) Bis (diphenylphosphino) ethane, copper (II) acetylacetonate, copper (II) acetate monohydrate, copper (II) acetate hydrate, copper 7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), copper bis (2,2,6,6-tetramethyl-3,5-heptanedionate ), Copper (I) bromide, copper (II) bromide dimethyl sulfide, copper (I) 1-butane thiolate, copper (II) Copper (II) chloride, copper (II) chloride dihydrate, copper (I) chloride-bis (lithium chloride), copper chromite, copper (I) cyanide, copper (I) cyanide di (II) cyclohexane butyrate, copper (II) 3,5-diisopropyl salicylate hydrate, copper (III) 2-ethylhexanoate, copper (II) Copper (II) formylate hydrate, copper (II) D-gluconate, copper (II) 1,2,3,4,8,9,10,11,15, (II) hexafluoroacetylacetonate hydrate, copper hydride, copper (II) hydroxide, copper (II) Copper (II) hydroxide, copper (II) hydroxide, copper (I) 3-methyl salicylate, copper (II) hydroxide, copper (II) hydroxide, copper (I) iodide, copper iodide dimethyl sulfide, Copper (II) nitrate, copper (II) nitrate hydrate, copper (I) oxide, copper (II) oxide, copper (II) perchlorate hexahydrate, copper (II) phthalocyanine , Copper phthalocyanine-3,4 ', 4' ', 4' '' - tetrasulfonic acid tetrasodium salt, copper (II) phthalocyanine- Copper (II) sulfate, copper (II) sulfate, copper (II) pyrosophosphate hydrate, copper (I) selenide, copper (II) selenite dihydrate, copper (I) thiophene-2-carboxylate, copper (II) sulfite, copper (II) Copper (II) trifluoroacetate, copper (II) trifluoroacetate, copper (II) trifluoromethanesulfonate, copper (I) trifluoro (I) trifluoromethanesulfonate toluene, copper-zinc alloy, cobalt (III) acetylacetonate, cobalt aluminum oxide, cobalt (II) benzoyl acetonate, cobalt Cobalt (II) bromide, cobalt (II) bromide hydrate, cobalt (II) carbonate hydrate, cobalt carbonyl, cobalt (II) chloride, cobalt (II) chloride hexahydrate, cobalt (II) chloride hexahydrate, Cobalt (II) cyanide dihydrate, cobalt (II) 2- ethylhexanoate, cobalt (II) fluoride, cobalt (II) fluoride tetrahydrate, cobalt (III) Cobalt (II) hydroxide, cobalt (II) iodide, cobalt (II) 2,3-naphthalocyanine, cobalt naphthenate, cobalt (II) nitrate hexahydrate, cobalt II) oxalate dihydrate, cobalt (II) oxide, cobalt (II, III) oxide, cobalt (II) -perchlorate hexahydrate, cobalt (II) phosphate hydrate, cobalt (II) phthalocyanine, cobalt (II) sulfate heptahydrate, cobalt (II) sulfate hydrate, cobalt (II) tetrafluoroborate hexahydrate, cobalt (II) thiocyanate, lithium, palladium, palladium (II) acetylacetonate, iron (III) acetate, nickel, nickel (II) acetate tetrahydrate, nickel (II) trifluoromethanesulfonate, nickel zinc iron oxide, iron Iron (III) bromide, iron (III) chloride, iron (II) chloride tetrahydrate, iron (III) bromide, (III) oxide, iron (III) oxide, indium, indium (III) oxide, iron (II) oxide, iron , Indium (III) can be selected from acetate hydrate, indium (III) acetylacetonate, zinc, zinc acetate, zinc acetate dihydrate, zinc acetylacetonate hydrate.

The polymer forming the cage effect is a copolymer capable of polyvalent ionic bond. Examples thereof include poly (acrylic acid), poly (acrylonitrile), poly (acrylonitrile-co-butadiene) (Acrylonitrile-co-butadiene), poly (acrylonitrile-co-butadiene) terminal-dicarboxylate, poly (acrylonitrile-co-methyl acrylate), poly (acrylamide) , Poly (acrylamide-co-acrylic acid) -partial sodium salt, poly (2-acrylamido-2-methyl-1-propanesulfonic acid), poly (2-acrylamido- (N-isopropylacrylamide), poly (N-isopropylacrylamide-co-acrylamide), alkali-soluble resins (alkali-soluble resins , ASR), and octa (polyglycidyl ether). However, One that does not.

Polymers for imparting flexibility include polymers such as LDPE, LLDPE, MDPE, PE, HDPE, polyurethane, PVC, silicone, ABS, latex, TPU (thermoplastic polyurethane), nylon, polyurethane, polyester, PET EPDM (ethylene-propylene rubber), EPM, MF (melamine-formaldehyde polymer), PAEK (polyacryl ether ketone) ), PAI (polyamideimide), PCT (poly (cyclohexanedimethylene terephthalate)), PCTFE (polychlorotrifluoroethylene), PDMS (polydimethylsiloxane), PEEK (polyetheretherketone), PEI Polyetherketone), PEK (polyetherketone ketone), PEN (poly (ethylene-2,6-naphthalene)), PEO (poly (ethylene oxide) (Poly (ethylene terephthalate ((PF (phenol-formaldehyde polymer), PHB (poly (2- (Polyimide), PIB (polyisobutylene), PMMA (polymethylmethacrylate), POD (polyoxadiazole), POD (POM), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polytetrafluoroethylene (PVA), polytetrafluoroethylene (POT) (PVDF), PVF (poly (vinyl fluoride)), SAN (polyvinylidene chloride), PVD (polyvinylidene chloride) (Styrene-acrylonitrile), SBR (styrene butadiene rubber), SMA (styrene maleic anhydride), SIR (styrene isoprene rubber), TPE (thermoplastic elastomer), TPI (thermoplastic polyimide), UF (urea formaldehyde polymer) UHMWPE (Ultra High Molecular Weight Polyethylene), UP (Unsaturated Polyester), VLDPE (Ultra Low Density Polyethylene), PAN (Polyacrylonite ), PBT (poly (butylene terephthalate)), ETFE (ethylene tetrafluoroethylene), EVA (ethylene-tetrafluoroethylene) Vinyl acetate), HIPS (high-impact polystyrene), PDVB (polydivinylbenzene), butadiene, polyisoprene, polyepoxy, acrylonitrile butadiene and polypropylene

Plasticizers for imparting flexibility include plasticizers such as phthalic acid plasticizers, phosphoric acid plasticizers, trimellitate plasticizers, aliphatic ester plasticizers, epoxides, ESO (epoxidized soybean oil) glycol esters, chlorinated paraffin, citric acid ELO (epoxidized linseed oil) (Dioctyl adipate), di-2-ethylhexyl phthalate, diisononyl phthalate, DOA (dioctyl adipate), di-2-ethylhexyl phthalate (Heptyl, nonyl) trimellitate, high molar mass benzyl phthalate, polyester of adipic acid, alkyl (meth) acrylate, Benzyl phthalate, butyl benzyl phthalate, 2-ethylhexyl diphenyl phosphate, TOTM (trioctyl trimellitate), DBP (dibutyl phthalate), DIDP (3-aminopropyl) triethoxysilane, an ester-based oil, glycerin (trimethylolpropane), dicyclohexyl phthalate, dodecyl phthalate, dodecyl phthalate), DOM (dioctyl maleate), citric acid ester, di (propylene glycol) dibenzoate, glycidoxypropyltrimethoxysilane, Ester fatty acid esters, polyhydric alcohol fatty acid, N-butylbenzene sulfonamide, trimethylol propane, neopentyl glycol, pentaerythritol, dioleic acid TMP tri-fatty acid ester, TMP-triolate, TMP-tri PE tetraoleate, PE tetra-oleate, TMP-complex ester, PE-complex ester methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl Oleate, methyl alkylation, n-butyl oleate, N-butyl stearate, I-octyl palmitate, I- I-octyl oleate, I-tridecyl stearate, lauryl oleate, di-i-octyl sebacate, di-i-tridecyl adipate, di- Melitate, and glycerol trioleate, and can be used within an environmental hormone tolerance range.

The composite material for 3D printing according to the present invention can be applied as a raw material that can be applied in a molten state rather than as a powder. In order to be printed in 3D, the raw material is supplied in the form of filament, and the rapid solidification after melting and discharging from the nozzle proceeds so that continuous coating can be performed between the layers.

The hardness of the polymer base of the filament for 3D printing produced by the composite material of the present invention is Shore A 90 or less. The melt index (190 占 폚, 2.16 kg) is 1 to 30 g / 10 min and the melt index (150 占 폚, 10 kg) is 3.0 g / 10 min or less.

The conductive parts manufactured by the method of the present invention can be applied to electrodes, sensors, wiring and the like of electronic devices, biosensors, chemical sensors, cell incubators, tissue engineering bioreactors, wearable devices, energy generation and storage devices .

The composite material of the present invention is formed by directly printing a circuit for fabricating a prototype of an electronic device designed for disposable use without using the etching method of a copper foil, thereby reducing the time required for research and development, cost reduction, It is possible to minimize the amount and minimize environmental pollution. In addition, coating materials for various medical diagnosis sensors and clothes such as blood pressure, blood vessel expansion degree, electrocardiogram, and the like worn on the human body, flexible displays, various actuators and sensors, speakers, keyboards, coated wires, filters, In the manufacture of plastic boxes and packaging boxes, hoses, cylinders, substrates, films, conductive tapes, all types of electrical terminals, etc., printed with shoes, smartphone cases, ornaments, mice, pads, o-rings, Can be used.

Another aspect of the present invention relates to a method for producing a cage comprising a carboxylic acid type, a sulfonic acid type, or a phosphonic acid type polyvalent base providing a cage effect, a carboxylic acid type, a sulfonic acid type or a phosphonic acid type polyvalent base providing the cage effect, The present invention relates to a method for producing an electronic part, which comprises 3D printing using a composite material comprising a hydrogen-bonding polymer forming a polymer complex and a metal precursor, and reducing the obtained printing material to form a conductive circuit and an electronic part will be.

In the method of the present invention, a film is prepared by blending a carboxylic acid type, a sulfonic acid type, or a phosphonic acid type polyvalent base and a metal precursor to provide a cage effect, and the film is crushed to a small size, A hydrogen-bonding polymer forming a bicomponent polymer complex by hydrogen bonding with a carboxylic acid group, a sulfonic acid group, a sulfonic acid group, or a phosphonic acid based polybasic group is mixed with a plasticizer and extruded into a filamentary form to prepare a composite material for 3D printing, The material can be manufactured as an electronic part by 3D printing, and then the electronic part can be reduced to form a conductive electronic part.

Alternatively, in the method of the present invention, a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polyvalent base providing cage effect, a carboxylic acid-based, sulfonic acid-based, or phosphonic acid- The hydrogen-bonding polymer forming the two-component polymer complex and the metal precursor are blended and then cast by solvent to be dried to obtain a film. The third polymer is then mixed with a plasticizer, And extruded into a filament to prepare a composite material for 3D printing. Then, the 3D compositing composite material is manufactured as an electronic component by 3D printing, and then the electronic component is reduced to form a conductive electronic component.

4 is a flow chart for explaining the manufacturing process of the composite material for 3D printing according to the present invention. 4, in the present invention, a carboxylic acid-based, sulfonic acid-, or phosphonic acid-based polyvalent base providing cage effect, a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polyvalent base and hydrogen The hydrogen-bonding polymer and the metal precursor forming the two-component polymer composite are combined, and the mixture is cast and solvent-dried to obtain a film (S110 to S130). The metal precursor that can be used in this step is not particularly limited but may be any metal precursors such as Group I, IIA, IIIA, IVA, etc. of gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, And VIIIB, may be used alone or in combination of two or more. The metal precursor may be an inorganic salt such as nitrate, sulfate, acetate, phosphate, silicate, hydrochloride and the like.

The solvent used in preparing the metal precursor solution may be a solvent capable of dissolving the metal precursor and capable of sufficiently swelling the polymer to penetrate the metal precursor into the filament. The solvent may be, for example, water; Amine based solvents; Ester solvents; Ketone solvents; Aliphatic or aromatic hydrocarbon solvents; Ether-based solvents; Alcohol solvents; Polyol solvents; Amide solvents; Sulfoxide solvents; Acetate solvents; Inorganic solvents; And mixtures thereof. For example, nitrile solvents such as acetonitrile, propionitrile, pentanenitrile, hexanenitrile, heptanenitrile, isobutylnitrile and the like; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and dodecane; Aromatic hydrocarbon solvents such as anisole, mesitylene and xylene; Ketone solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone and acetone; Ether solvents such as tetrahydrofuran, diisobutyl ether and isopropyl ether; Ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and the like; Alcohol solvents such as isopropyl alcohol, butyl alcohol, hexyl alcohol and octyl alcohol; Inorganic solvents; Or a mixture thereof, but are not limited thereto. As the solvent, a mixed solvent of two or more of them may be used. The metal precursor solution may have a concentration ranging from 3 to 30% by weight (S120).

As a method for three-dimensional printing, a UV precision lamination method in which a low-viscosity UV-curable material is injected and laminated at a predetermined height and a thermoplastic filament having a diameter of 1.75 mm are melted at a temperature of 130 to 250 ° C, FDM (Fused Deposition Modeling) method in which a plurality of layers are stacked in a thickness of 1 mm. In the case of the FDM method, the 3D structure to be manufactured is first modeled by a 3D CAD program, a standard interface data format used in the 3D CAD system is generated, and the 3D structure is divided into layers and sliced. Then, the three-dimensional structure to be fabricated is printed and laminated on each layer by using an FDM-type three-dimensional printer. Referring to FIG. 1, a schematic structure of an FDM-type three-dimensional printer will be described. A filament for FDM formed of a thermoplastic polymer is supplied to a three-dimensional printer, and melts filaments in an extruder to inject melted filaments through nozzles. At this time, in order to stack the three-dimensional structures on the respective layers according to the designed data, the three-dimensional printer is provided with a transfer device for transferring the extruder vertically and horizontally. The bottom plate of the 3D printer moves in the Y-axis, the printing head moves in the X-axis, one layer is stacked, the other layer is raised in the Z-axis and then the X and Y axes are moved as described above. Layer printing is performed in such a manner that the layer is raised. When a three-dimensional printer is layered and cured by layer-by-layer printing, an electronic component having a three-dimensional solid shape can be manufactured (S150).

Then, the metal precursor in the laminated layer is reduced to metal (S150). The metal precursor impregnated in the filament can be reduced to a metal by treatment with a reducing agent. Chemical reduction methods include, but are not limited to, potassium sodium tartrate hydrate (Rochelle Salt), hydroxylamine hydrochloride ethylamine, ethanolamine, triethylamine, ethylamine, glucose, formic acid, hydrazine, isopropanol, acetone, ethanol, sodium borohydride, Dehydrogenase, borane, catechol borane solution, steam reduction, precipitation reduction and spray reduction method. In the reducing step, only a specific portion of the printed part may be selectively reduced to form a conductive pattern.

The reduction method can be carried out, for example, by exposing a filament impregnated with a metal precursor to a hydrazine (N2H4) vapor, dripping concentrated hydrazine (N2H4) on the filament, or immersing the filament in an ethanol solution of sodium borohydride The metal precursor in the print can be reduced to metal. At this time, the metal precursor present on the surface of the filament can also be reduced to metal. On the other hand, after the filament is treated with a reducing agent, washing and drying steps can be further performed. Also, by repeating the immersion, drying, and reduction steps, metal metal precursors may be dispersed in the filament at a high density to improve the conductive percolation network.

Another aspect of the present invention relates to a 3D-shaped electronic component including a conductive pattern, which is manufactured by the manufacturing method of the present invention. Such electronic components include electronic devices, biosensors, chemical sensors, cell incubators, tissue engineering bioreactors, wearable devices, electrodes for energy generation and storage devices, sensors, wiring, and the like.

Hereinafter, the present invention will be described in more detail with reference to various embodiments, but the technical idea of the present invention is not limited by the following embodiments.

Example  One

8 g of polyacrylic acid, 2 g of AgNO3 and 7 g of polylactic acid (PLA) were dissolved in 30 g of tetrahydrofuran and heated at 30 DEG C for 30 minutes to form a polymer metal complex solution. This solution was evaporated using a rotary evaporator to obtain a polymer metal complex film. 17 g of the obtained polymer metal complex film and 1 g of triethyl citrate as a plasticizer were uniformly mixed, and then the mixture was put into a mini extruder and extruded at 200 ° C to obtain a 1.75 mm filament. Using the obtained filament, a desired two-dimensional circuit was formed by 3D printing, followed by reduction in a 10% hydrazine solution for 10 minutes, followed by heat treatment and drying at 100 ° C for 10 minutes to form a conductive circuit pattern.

Example  2

Instead of polyacrylic acid, 8 g of perfluoroglutaric acid and 2 g of silver tribromoacetate were dissolved in 10 g of DMF and 3 g of ethyl acetate at 30 DEG C to form a metal composite solution, thereby preparing filaments And then subjected to 3D printing to obtain a conductive pattern.

Example  3

10 g of 1,3-adamantanedioic acid and 2 g of silver tribromoacetate were dissolved in 3 g of DMF and 5 g of dimethylethylketone and heated at 40 ° C for 50 minutes to form a polymer metal complex solution. This solution was evaporated by using a rotary evaporator to obtain a metal composite film. 12 g of the obtained polymer metal complex film, 7 g of polylactic acid (PLA) and 1 g of triethyl citrate as a plasticizer were uniformly mixed and then extruded into a mini extruder at 200 ° C. to prepare a 1.75 mm filament. Using the obtained filament, a desired two-dimensional circuit was formed by 3D printing, followed by reduction in a 10% hydrazine solution for 10 minutes, followed by heat treatment and drying at 100 ° C for 10 minutes to form a conductive circuit pattern.

Example  4

8 g of polyacrylic acid, 2 g of silver tribromoacetate and 7 g of polylactic acid (PLA) were dissolved in 30 g of tetrahydrofuran and heated at 30 ° C for 30 minutes to form a polymer metal complex solution. This solution was evaporated using a rotary evaporator to obtain a polymer metal complex film. 17 g of the obtained polymer metal composite film and 3 g of polyethylene as a polymer for imparting flexibility were uniformly mixed and then extruded into a mini extruder at 200 ° C. to obtain a 1.75 mm filament. Using the obtained filament, a desired two-dimensional circuit was formed by 3D printing, followed by reduction in a 10% hydrazine solution for 10 minutes, followed by heat treatment and drying at 100 ° C for 10 minutes to form a conductive circuit pattern.

Example  5

8 g of triphosphoric acid, 2 g of kappa trifloromethanesulfonate and 7 g of polylactic acid (PLA) were dissolved in 20 g of tetrahydrofuran and 10 g of ethylacetate and heated at 30 DEG C for 30 minutes to form a polymer metal complex solution. This solution was evaporated using a rotary evaporator to obtain a polymer metal complex film. 17 g of the obtained polymer metal composite film and 3 g of polyethylene as a polymer for imparting flexibility were uniformly mixed and then extruded into a mini extruder at 200 ° C. to obtain a 1.75 mm filament. Using the obtained filament, a desired two-dimensional circuit was formed by 3D printing, followed by reduction in a 10% hydrazine solution for 30 minutes, followed by heat treatment and drying at 100 ° C for 10 minutes to form a conductive circuit pattern.

Comparative Example  One

In Example 1, 8 g of polyacrylic acid, 8 g of ABS, 4 g of AgNO 3, 7 g of polylactic acid (PLA) and 1 g of triethyl citrate as a plasticizer were uniformly mixed and then extruded into a mini extruder at 200 ° C to obtain a 1.75 mm filament. Using the obtained filament, a desired two-dimensional circuit was formed by 3D printing.

Comparative Example  2

60 parts by weight of acrylonitrile-butadiene styrene (ABS) as a thermoplastic resin, 30 parts by weight of carbon black (Korea Carbon Black, trade name: HIBLACK 40B2) as a plasticizer and 5 parts by weight of diisooctyl phthalate were mixed with 5 parts by weight of DBK- And 35 parts by weight of dispersed carbon black, which had been subjected to sublimation three times, were extruded with a mini extruder to prepare filaments having a diameter of 1.75 mm. Using this conductive filament, 3D printing as in Example 1 was performed to form a desired two-dimensional circuit.

Resistance (ohm / cm) Conductive material
Content (wt%) Clogging of printing nozzle Printing Temperature (℃) Example 1 320 11.1 Within 5 hours None 190 Example 2 310 11.1 Within 5 hours None 210 Example 3 130 10.5 Within 5 hours None 220 Example 4 530 10.0 Within 5 hours None 230 Example 5 250 10.0 Within 5 hours None 190 Comparative Example 1 12 (M [Omega] / cm) 20.0 Clogged in 30 minutes 230 Comparative Example 2 130 30.0 Clogged within 1 hour 240

 1, a carboxylic acid type, a sulfonic acid type, or a phosphonic acid type polyvalent base which provides a cage effect according to the present invention, a carboxylic acid type, a sulfonic acid type, or a phosphonic acid type polyvalent base and a hydrogen bond (Examples 1 to 5) in the case of a filament made by a composite material for 3D printing comprising a hydrogen-bonding polymer forming a two-component polymer composite and a metal precursor, a material including a polymeric binder and metal nanoparticles and carbon black (Comparative Examples 1 and 2) produced by the present invention exhibited excellent conductivity in spite of the fact that only 1/2 to 1/3 of the filler was used, and there was no clogging of the nozzle upon filament extrusion, It is possible to confirm that the quality of post-processing can be improved because the flexibility and mechanical properties of the filaments are excellent.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, scope, and equivalence of the claims of the Korean Intellectual Property Office are included in the scope of the present invention Should be interpreted.

Claims (22)

A polybasic acid-based polybasic acid which provides a cage effect, a carboxylic acid-based, a sulfonic acid-based, or phosphonic acid-based polyvalent base which provides the cage effect, A composite material for 3D printing comprising a polymer having a hydrogen bond and a metal precursor.
The method of claim 1, wherein the metal precursor is selected from the group consisting of gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, cobalt, lithium, zirconium, lead, tin, titanium, molybdenum, tungsten, Tantalum, vanadium, chromium, niobium, aluminum, and magnesium.
The polymer according to claim 1, wherein the polymer having hydrogen bonds is selected from the group consisting of PAA (poly (acrylic acid)), PLA (polylactic acid), polyamide, polyester, aramid, polyvinyl, cellulose, polyurethane, collagen, silk, PVPh (Polyvinyl alcohol), PVP (polyvinyl alcohol), PVP (poly (vinylphenol), P2VP (poly (2-vinylpyridine) ), PHV (poly (3-oxy)), PGA (polyglycolic acid), PEG (polyethylene glycol), PEO (poly (ethylene oxide)), PPG (polypropylene glycol), PTMG (polytetramethylene glycol) , PCL (poly (3-caprolactone)) TDP (4,4'-thiodiphenol), PMVT (poly (4-methyl-5-vinylthiazole) (Poly (N-acryloyl-N'-phenylpiperazine)), PSSA (poly (styrenesulfonic acid) Vinyl pyridine), PVP (poly (N-vinyl-2-pyrrolidone)), PMVAc (2-ethyl-2-oxazoline), DMBVPh (poly (2,3-dimethylbutadiene stat-4-vinylphenol) ), PAMAs (poly (N-alkyl methacrylate) S, PDIS (poly (dialkyl itaconate) s), poly (methoxycarbonylmethyl methacrylate), EVA (ethylene / vinyl acetate) EVAL (ethylene / vinyl alcohol), DDA (dodecanedioic acid) DMBAMA (2,3-dimethylbutadiene STAT-4-vinylphenol), (poly (styrene- (Polyvinyl acetate-co-vinyl alcohol), PAPP (poly (N-acryloyl-N'-phenylpiperazine)), PAS (poly (p-acetoxystyrene) ), PBAAA (poly (butyl acrylate-co-acrylic acid)), PBMA (poly (n-butyl methacrylate)), PCHMA (poly (cyclohexyl methacrylate) (N, N-dimethylacrylamide)), PDMA (poly (N, N-dimethylacrylamide) ), PEMA (poly (ethyl methacrylate)), PLLA (poly (L-lactide)), PMMA (polymethyl methacrylate), PMMAA (poly (methyl methacrylate- Poly (styrene-co-acrylic acid), PSA (polystyrene), PSSA (polyoxyethylene), PP (polypropylene) PVA (poly (vinyl acetate)), PVDF (poly (vinylidene fluoride)), PVME (poly (vinyl methyl ether) (PVPA), PVPy (poly (4-vinylpyridine)), SBA (suberic acid), SCA (succinic acid) STVPh (styrene / vinylphenol), SVBDEP 4-vinylbenzenephosphonic acid diethyl ester), isotactic VBDEP (4-vinylbenzenephosphonic acid ethyl ester) VPH (4-vinylphenol), aPHB (atactic poly (3-hydroxy)), aPMMA Methyl methacrylate), iPHB (poly (3-hydroxy)), iPMMA Wherein the matrix is selected from the group consisting of tantalum polymethyl methacrylate, sPHB (syndiotactic poly (3-hydroxy)), sPMMA (syndiotactic polymethylmethacrylate).
The composite material for 3D printing according to claim 1, wherein the two-component polymer composite is a hydrogen bonding interpolymer complex between a polyacid and a polybase.
The bicomponent polymer composite according to claim 1, wherein the two-component polymer composite is at least one selected from the group consisting of polyacrylic acid (PAA), polymethacrylic acid (PMMA), 1,3-adamantanedioic acid, 1,3-adamantanedicarboxylic acid, Dicarboxylic acid, bis (carboxymethyl) trithiocarbonate, 2-bromoterephthalic acid, 1, 2'-dicarboxylic acid, Cyclohexanedicarboxylic acid, trans-1,2-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, , 3-cyclohexane dicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, cyclohexyl succinic acid, trans-DL-1,2-cyclopentanedicarboxylic acid, dibromomaleic acid, 3-dibromosuccinic acid, 4,5-dichlorophthalic acid, diethylmalonic acid, 3,4-dihydroxyhydrocinnamic acid, 2,5-dihydroxyterephthalic acid, Dimer acid, docosanoic acid, ethyl 2-methoxyisophthalic acid, 4-methylphthalic acid, 6-methylpyridine-2,3-dicarboxylic acid, 2-methoxybenzoic acid, Acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, exo-5-norbonenecarboxylic acid, 4,4'-oxybis (benzoic acid), perfluoroglutaric acid, 1,4-phenylenedipropionic acid, 3-phenylglutaric acid, phenylmalonic acid, 5-sulfoisophthalic acid monolithium salt, 4,4'-sulfonyldibenzoic acid, 4-sulfophthalic acid, sulfosuccinic acid, terephthalic acid, 4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetic acid tetrahydrochloride hydrate, tetrafluoroisophthalic acid, tetrafluorophthalic acid, 3-thiophenemalonic acid, 1,2,3 -Triazole-4,5-dicarboxylic acid, cis, cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid, undecanedioic acid, polystyrene sulfonic acid, 1,1 , 2,2-tetrafluoro Sulfonic acid, sulfoacetic acid ethanesulfonic acid, 3-hydroxypropane-1-sulfonic acid, 1,3-propanedisulfonic acid, potassium nonafluoro-1-butanesulfonate, nonafluorobutane- (Trimethylsilyl) ethanesulfonic acid sodium salt, tridecaprylohexane-1-sulfonic acid potassium salt, hydroxyquinone sulfonic acid potassium salt, benzenesulfonic acid , 1-naphthalenesulfonic acid, and dodecylbenzene-sulfonic acid, which are selected from the group consisting of a phosphoric acid, a triphosphoric acid, a polyphosphoric acid, a polyphosphate, a cyclic trimethylphosphate, adenosine diphosphate, adenosine prephosphate A hydrogen bond between a polyacid and a polybase selected from the group consisting of polylactic acid, polyethylene oxide, polyacrylamide, poly (N-vinylpyrrolidone) polyurethane, polyurea, Wherein the composite material is a hydrogen bonding interpolymer complex.
The polybasic compound as claimed in claim 1, wherein the polyvalent base forming the cage effect is a polymer capable of polyvalent ionic bonding, and is selected from the group consisting of poly (acrylic acid), poly (acrylonitrile), poly (acrylonitrile-co-butadiene) (Acrylonitrile-co-butadiene), poly (acrylonitrile-co-butadiene) end-dicarboxylate, poly (acrylonitrile-co-methyl acrylate) Acrylic acid), poly (acrylamide-co-acrylic acid) -partial sodium salt, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (N-isopropylacrylamide), poly (N-isopropylacrylamide-co-acrylamide), alkali soluble resins (ASR ), Octa (polyglycidyl ether), polyurethane, poly (methyl methacrylate), poly Alkylenedioxy) thiophene, 3D printing for composite materials, characterized in that selected from the group consisting of polyethylene, and polypropylene.
The composite material according to claim 1, wherein the composite material is selected from the group consisting of LDPE, LLDPE, MDPE, PE, HDPE, polyurethane, PVC, silicone, ABS, latex, TPU (thermoplastic polyurethane), nylon, polyurethane, EPDM (ethylene-propylene rubber), EPM, MF (melamine-formaldehyde polymer), PAEK (polyacryletherketone), PET, natural rubber (NR), butadiene, CR, BR, EPDM , Polyamideimide (PAI), poly (cyclohexanedimethylene terephthalate), PCTFE (polychlorotrifluoroethylene), PDMS (polydimethylsiloxane), PEEK (polyetheretherketone), PEI PEK (polyether ketone), PEN (poly (ethylene-2,6-naphthalene)), PEO (poly (ethylene oxide)), PES (polyether sulfone), PET Poly (ethylene terephthalate ((PF (phenol-formaldehyde polymer), PHB (poly (2-hydroxy) (Polyimide), PIB (polyisobutylene), PMMA (polymethyl methacrylate), POD (polyoxadiazole), POM (polyoxymethylene) ), POP (polyoxypropylene), PPO (poly (phenylene oxide)), PPS (poly (phenylene sulfide)), PTFE (polytetrafluoroethylene), PVA Acetate), PVB (polyvinyl butyral), PVDC (polyvinylidene chloride), PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride), SAN (styrene-acrylonitrile ), UF (urea formaldehyde polymer), UHMWPE (ultra high molecular weight polyethylene), SBR (styrene butadiene rubber), SMA (styrene maleic anhydride), SIR (styrene isoprene rubber), TPE (thermoplastic elastomer) ), UP (unsaturated polyester), VLDPE (ultra low density polyethylene), PAN (polyacrylonitrile), PAS Poly (butylene terephthalate), ETFE (ethylene tetrafluoroethylene), EVA (ethylene-vinyl acetate), HIPS (high- Characterized in that it further comprises at least one flexibility imparting polymer selected from the group consisting of poly (vinylidene fluoride), poly (vinylidene fluoride), poly (vinylidene chloride), polystyrene, impact polystyrene), PDVB (polydivinylbenzene), butadiene, polyisoprene, polyepoxy, acrylonitrile butadiene and polypropylene Composite for printing.
The composite material according to claim 1, wherein the composite material is selected from the group consisting of a phthalic acid plasticizer, a phosphoric acid plasticizer, a trimellitate plasticizer, an aliphatic ester plasticizer, an epoxy, an ESO (epoxidized soybean oil) glycol ester, chlorinated paraffin, citric acid ELO (epoxidized linseed oil) , Polyester plasticizer, trimellate, triacetin, triethyl citrate, DOP (phthalic acid dioctyl) diphenyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dioctyl adipate, di- (Heptyl, nonyl) trimellitate, high molar mass benzyl phthalate, polyester of adipic acid, alkyl benzyl phthalate, di (heptyl, nonyl) adipate, Butyl benzyl phthalate, ethylhexyldiphenyl phosphate, TOTM (trioctyltrimellitate), DBP (dibutyl phthalate), DIDP (diisodecyl phthalate ), DOM (dioctyl maleate), citric acid ester, di (propylene glycol) dibenzoate, glycidoxypropyltrimethoxysilane, (3-aminopropyl) triethoxysilane, ester oils, phthalic acid series plasticizers , Triglyceride ester oil, monohydric alcohol fatty acid ester, polyhydric alcohol fatty acid, N-butylbenzenesulfonamide, trimethylol propane, neopentyl glycol, pentaerythritol, NPG dioleate TMP tri-fatty acid ester, TMP- TMP-trioleate, PE tetraester, PE tetra-fatty acid ester, PE tetraoleate, TMP-complex ester, PE-complex ester methyl laurate, methyl myristate, methyl palmitate, methyl stearate, Methyl alkylation, n-butyl oleate, N-butyl stearate, I-octyl palmitate, I-octyl stearate, Di-i-tridecyl adipate, di-i-octyl maleate, a gradual di-oleate, tri-i-tridecyl stearate, lauryl oleate, di- Wherein said plasticizer further comprises a plasticizer selected from the group consisting of glycerin, triethylene glycol, decyl trimellitate, glycerin, and triolate.
The composite material for 3D printing according to claim 1, wherein the composite material comprises 3 wt% to 30 wt% of a metal precursor based on 100 wt% of the total composite material.
A carboxylic acid-based, phosphonic acid-based, or phosphonic acid-based polyvalent base that provides a cage effect, a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polyvalent base that provides the cage effect, hydrogen Wherein the conductive material is formed by 3D printing using a composite material comprising a binder polymer and a metal precursor, and then reducing the obtained printing material to form a conductive electronic part.
11. The method of claim 10,
Preparing a film by blending a carboxylic acid type, a sulfonic acid type, or a phosphonic acid type polyvalent base and a metal precursor to provide a cage effect;
After the film is pulverized to a small size, a hydrogen-bonding polymer forming a two-component polymer composite by hydrogen bonding with a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polybasic base that provides the cage effect is mixed with a plasticizer, Preparing a composite material for 3D printing by extrusion;
Fabricating the composite material for 3D printing as an electronic component by 3D printing;
And reducing the electronic component to form a conductive electronic component.
11. The method of claim 10,
A carboxylic acid-based, phosphonic acid-based, or phosphonic acid-based polyvalent base that provides a cage effect, a carboxylic acid-based, sulfonic acid-based, or phosphonic acid-based polyvalent base that provides the cage effect, hydrogen Blending the binder polymer and the metal precursor to produce a film;
Preparing a composite material for 3D printing by mixing the polymer with a plasticizer that imparts flexibility to the film after the film is crushed to a small size, and extruding the mixed material into a filament;
Fabricating the composite material for 3D printing as an electronic component by 3D printing;
And reducing the electronic component to form a conductive electronic component.
The method of claim 10, wherein the metal precursor is selected from the group consisting of gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, cobalt, lithium, zirconium, lead, tin, titanium, molybdenum, tungsten, Wherein an inorganic salt or an organic salt of a metal selected from tantalum, vanadium, chromium, niobium, aluminum and magnesium is used.
11. The method of claim 10, wherein the bicomponent polymer composite is a hydrogen bonding interpolymer complex between a polyacid and a polybase.
11. The polymer composite according to claim 10, wherein the two-component polymer composite is selected from the group consisting of PAA (poly (acrylic acid)), PLA (polylactic acid), polyamide, polyester, aramid, polyvinyl, cellulose, polyurethane, collagen, silk, PVPh (Polyvinyl alcohol), PVP (polyvinyl alcohol), PVP (poly (vinylphenol), P2VP (poly (2-vinylpyridine) ), PHV (poly (3-oxy), PGA (polyglycolic acid), PEG (polyethylene glycol), PEO (poly (ethylene oxide)), PPG (polypropylene glycol), PTMG (polytetramethylene glycol) (PVPA), poly (vinylphosphonic acid), PAPP (poly (3-caprolactone)) TDP (4,4'-thiodiphenol), PMVT Poly (N-acryloyl-N'-phenylpiperazine)), PSSA (poly (styrene sulfonic acid) Pyridine), PVP (poly (N-vinyl-2-pyrrolidone)), PMVAc (poly (2-ethyl-2-oxazoline), DMBVPh (poly (2,3-dimethylbutadiene stat-4-vinylphenol) ), PAMAs (poly (N-alkyl methacrylate) S, PDIS (poly (dialkyl itaconate) s), poly (methoxycarbonylmethyl methacrylate), EVA (ethylene / vinyl acetate) EVAL (ethylene / vinyl alcohol), DDA (dodecanedioic acid) DMBAMA (2,3-dimethylbutadiene STAT-4-vinylphenol), (poly (styrene- (Polyvinyl acetate-co-vinyl alcohol), PAPP (poly (N-acryloyl-N'-phenylpiperazine)), PAS (poly (p-acetoxystyrene) ), PBAAA (poly (butyl acrylate-co-acrylic acid)), PBMA (poly (n-butyl methacrylate)), PCHMA (poly (cyclohexyl methacrylate) (N, N-dimethylacrylamide)), PDMA (poly (N, N-dimethylacrylamide) ), PEMA (poly (ethyl methacrylate)), PLLA (poly (L-lactide)), PMMA (polymethyl methacrylate), PMMAA (poly (methyl methacrylate- Poly (styrene-co-acrylic acid), PSA (polystyrene), PSSA (polyoxyethylene), PP (polypropylene) PVA (poly (vinyl acetate)), PVDF (poly (vinylidene fluoride)), PVME (poly (vinyl methyl ether) (PVPA), PVPy (poly (4-vinylpyridine)), SBA (suberic acid), SCA (succinic acid) STVPh (styrene / vinylphenol), SVBDEP 4-vinylbenzenephosphonic acid diethyl ester), isotactic VBDEP (4-vinylbenzenephosphonic acid ethyl ester) VPH (4-vinylphenol), aPHB (atactic poly (3-hydroxy)), aPMMA Methyl methacrylate), iPHB (poly (3-hydroxy)), iPMMA Tactic polymethylmethacrylate), sPHB (syndiotactic poly (3-hydroxy)), and sPMMA (syndiotactic polymethylmethacrylate). A method of manufacturing an electronic component.
16. The method according to claim 15, wherein the polymer forming the cage effect is a polymer capable of polyvalent ionic bonding and is selected from the group consisting of poly (acrylic acid), poly (acrylonitrile), poly (acrylonitrile-co-butadiene) (Acrylonitrile-co-butadiene), poly (acrylonitrile-co-butadiene) end-dicarboxyl, poly (acrylonitrile-co-methyl acrylate) poly (acrylamide) ), Poly (acrylamide-co-acrylic acid) -partial sodium salt, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (N-isopropylacrylamide), poly (N-isopropylacrylamide-co-acrylamide), alkali soluble resins (alkali soluble Resin, ASR), and octa (polyglycidyl ether), polyurethane, and poly Methacrylate), poly (alkylenedioxy) thiophene, a method of manufacturing an electronic part, characterized in that selected from the group consisting of polyethylene, and polypropylene.
12. The method of claim 11, wherein the polymer imparting flexibility is at least one selected from the group consisting of LDPE, LLDPE, MDPE, PE, HDPE, polyurethane, PVC, silicone, ABS, latex, TPU (thermoplastic polyurethane), nylon, polyurethane (Ethylene-propylene-diene monomer), EPR (ethylene-propylene rubber), EPM, MF (melamine-formaldehyde polymer) Polyetheretherketone (PAEK), polyamideimide (PAI), poly (cyclohexanedimethylene terephthalate), PCTFE (polychlorotrifluoroethylene), PDMS (polydimethylsiloxane) (PEEK), PEK (polyetherketone), PEKK (polyetherketone ketone), PEN (poly (ethylene-2,6-naphthalene)), PEO (poly (ethylene oxide) ), PET (poly (ethylene terephthalate ((PF (phenol-formaldehyde polymer), PHB (Poly (2-hydroxy)), PHVB (poly (3-hydroxy-valerate), PI (polyimide), PIB (polyisobutylene), PMMA (polymethyl methacrylate) (Polyoxymethylene), POP (polyoxypropylene), PPO (poly (phenylene oxide)), PPS (poly (phenylene sulfide)), PTFE (polytetrafluoroethylene), PVA Polyvinyl alcohol), PVAC (poly (vinyl acetate)), PVB (polyvinyl butyral), PVDC (polyvinylidene chloride), PVDF (poly (vinylidene fluoride) ), SAN (styrene-acrylonitrile), SBR (styrene butadiene rubber), SMA (styrene maleic anhydride), SIR (styrene isoprene rubber), TPE (thermoplastic elastomer), TPI (thermoplastic polyimide) UHMWPE (Ultra High Molecular Weight Polyethylene), UP (Unsaturated Polyester), VLDPE (Ultra Low Density Polyethylene), PAN Polybutylene terephthalate), ETFE (ethylene tetrafluoroethylene), EVA (ethylene-vinyl acetate), polyvinylidene fluoride (PVP) Wherein at least one selected from the group consisting of HIPS (high-impact polystyrene), PDVB (polydivinylbenzene), butadiene, polyisoprene, polyepoxy, acrylonitrile butadiene and polypropylene is used. ≪ / RTI >
12. The method of claim 11, wherein the plasticizer is selected from the group consisting of a phthalic acid plasticizer, a phosphoric acid plasticizer, a trimellitate plasticizer, an aliphatic ester plasticizer, an epoxy, an ESO (epoxidized soybean oil) glycol ester, chlorinated paraffin, citric acid ELO (epoxidized linseed oil) (Meth) acrylate, a polyester plasticizer, trimellate, triacetin, triethyl citrate, DOP (phthalic acid dioctyl) diphenyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dioctyl adipate, (Heptyl, nonyl) trimellitate, high molar mass benzyl phthalate, polyester of adipic acid, alkyl benzyl phthalate, butyl (heptyl, nonyl) adipate, di Benzyl phthalate, ethylhexyldiphenyl phosphate, TOTM (trioctyl trimellitate), DBP (dibutyl phthalate), DIDP (diisodecyl phthalate), (3-aminopropyl) triethoxysilane, ester-based oils, phthalic acid-based plasticizers, glycerin-based plasticizers such as DOM (dioctyl maleate), citric acid ester, di (propylene glycol) dibenzoate, glycidoxypropyltrimethoxysilane, TMP-triallylate, TMP-trilaurate, TMP-trilaurate, TMP-trilaurate, TMP-triolate, But are not limited to, trioleate, PE tetraester, PE tetra-fatty acid ester, PE tetraoleate, TMP-complex ester, PE-complex ester methyl laurate, methyl myristate, methyl palmitate, methyl stearate, , n-butyl oleate, N-butyl stearate, I-octyl palmitate, I-octyl stearate, Di-i-tridecyl adipate, di-i-octyl maleate, a gradual di-oleate, tri-i-tridecyl stearate, lauryl oleate, di- Decyltrimellitate, glycerin, and triolate is used as a solvent for the electronic component.
The method of claim 1, wherein the composite material comprises 3 to 30% by weight of a metal precursor based on 100% by weight of the total composite material.
The manufacturing method of an electronic device according to claim 10, wherein the step of 3D printing of the electronic part is a step of molding the 3D electronic part by injecting the 3D printing composite material into a FDM (Fused Deposition method) .
The method of claim 10, wherein the reducing step is a step of reducing the reducing agent to a reducing agent selected from the group consisting of hydrazine, hydrazine hydrate, sodium borohydride, formic acid, oxalic acid, ascorbic acid, and lithium aluminum hydride. Of the electronic component.
A 3D shape electronic component comprising a conductive pattern, which is produced by the manufacturing method of any one of claims 10 to 21.

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