WO2014104737A1 - Composition d'encre métallique à faible viscosité, et carte de circuits imprimés l'utilisant - Google Patents

Composition d'encre métallique à faible viscosité, et carte de circuits imprimés l'utilisant Download PDF

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Publication number
WO2014104737A1
WO2014104737A1 PCT/KR2013/012164 KR2013012164W WO2014104737A1 WO 2014104737 A1 WO2014104737 A1 WO 2014104737A1 KR 2013012164 W KR2013012164 W KR 2013012164W WO 2014104737 A1 WO2014104737 A1 WO 2014104737A1
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Prior art keywords
metal
ink composition
low viscosity
metal ink
nanoparticles
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PCT/KR2013/012164
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English (en)
Korean (ko)
Inventor
박한성
이현진
유의덕
김우정
유정섭
Original Assignee
주식회사 두산
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Publication of WO2014104737A1 publication Critical patent/WO2014104737A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1157—Using means for chemical reduction
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing

Definitions

  • the present invention relates to a low-viscosity metal ink composition capable of forming a thin film circuit pattern having high conductivity while having excellent adhesion to a substrate without a surface treatment process of the substrate, and a printed white substrate using the same.
  • PCBs printed circuit boards
  • FPCBs flexible printed circuit boards
  • etching processes on copper clad laminates, CCDs, or flexible copper clad laminates (FCCL). It is manufactured by forming a pattern through.
  • the metal wiring layer is formed in a board
  • the conventional conductive paste it is applied to a specific printing process such as screen printing requiring high viscosity by adding an epoxy resin-based binder resin that can secure the adhesive force, there is a limit in the implementation of a fine circuit pattern.
  • Low-viscosity conductive In the case of ink, a metal thin film coating is performed using a process such as inkjet or microgravure. In addition, the low viscosity of the ink is required due to the characteristics of the metal thin film implementation process by the direct printing method. Since the epoxy resin-based binder resin has a high viscosity, the physical properties of the ink such as low viscosity can be secured while ensuring reliability such as adhesive strength.
  • the surface energy or surface roughness of the substrate by using a chemical treatment method such as physical treatment such as plasma treatment, corona discharge, or etching with an alkaline solution, etc.
  • a chemical treatment method such as physical treatment such as plasma treatment, corona discharge, or etching with an alkaline solution, etc.
  • the surface treatment process of such a substrate has a limit in improving the interlayer adhesion between the metal wiring layer and the substrate, so that a separate adhesive layer is required, and there is a limitation in applying it to products requiring high reliability thermally and chemically. .
  • Korean Patent Laid-Open No. 1 2011 ⁇ 0002917 discloses a surface treatment method of a substrate using a hydrocarbon-based pressure-sensitive adhesive composition.
  • the surface of the substrate is modified by the hydrocarbon-based pressure-sensitive adhesive composition, thereby improving the interlayer adhesion between the metal wiring layer and the substrate.
  • the present invention provides a low viscosity metal ink composition capable of forming a thin-film circuit pattern having excellent adhesion properties to a substrate without heat treatment, surface resistance, corrosion resistance, adhesion reliability, and flexibility, and a printed circuit using the same. To provide a substrate.
  • the invention (a) (: ⁇ (: carboxylate-based ligand and a C 5 ⁇ the metal nanoparticles capped by a primary amine-based ligands of the C 20 of 20; (b) non-polar organic solvent; (c) an epoxy resin It provides a low viscosity metal ink composition comprising (d) a curing agent, (e) a mixed ether solvent containing an aromatic ether solvent and an aliphatic ether solvent, and (f) a dispersant.
  • the present invention also provides a printed circuit board comprising a circuit layer formed of the low viscosity metal ink composition described above.
  • the low viscosity metal ink composition according to the present invention has excellent dispersion stability and adhesion characteristics, it is possible to implement a fine thin film circuit pattern having excellent adhesion characteristics without a surface treatment process of a substrate.
  • the circuit layer of the printed circuit board formed of the low viscosity metal ink composition of the present invention is not only excellent in heat resistance, corrosion resistance and bendability, but also excellent in adhesion to the substrate.
  • Figure 2 is a transmission electron microscope (Transmission Electron Microscope, TEM) of the silver nanoparticles prepared in Preparation Example 6.
  • Figure 3 is a photograph of the metal ink composition of Example 1 before and after the heat treatment, and before and after repeating five cross-cut (cross-cut) test according to ASTM D 3359.
  • the present invention is a low-viscosity metal ink composition which forms a conductive circuit through a direct printing method, which is capped by (a) ( ⁇ ⁇ (: 20 carboxylate ligand and C 5 ⁇ C 20 primary amine ligand Metal nanoparticles; (b) apolar organic solvents; (c) epoxy resins; (d) curing agents; (e) mixed ether solvents containing aromatic ether solvents and aliphatic ether solvents; and (f) dispersants.
  • the low-viscosity metal ink composition has excellent dispersion stability and can realize a uniform thin film circuit pattern, and has excellent adhesive strength with the substrate even without surface treatment of the substrate, and has excellent heat resistance, corrosion resistance, and bone staining property.
  • a thin film circuit pattern can be formed.
  • the metal nanoparticles are nano-sized metal particles that are capped by a C: 20 carboxylate ligand and a C 5 to C 20 primary amine ligand.
  • both the carboxylate ligand and the primary amine ligand are bound or adsorbed to the particle surface during the preparation of the metal nanoparticles, thereby preventing the aggregation between particles due to surface instability (capping Hgand) to increase the dispersibility )to be.
  • capping Hgand surface instability
  • the primary amine ligand of the capping ligand may cure the epoxy resin.
  • the metal nanoparticles capped by the primary amine ligand may self-disperse in a nonpolar organic solvent because of the primary amine ligand.
  • the primary amine ligand is excellent in compatibility with a mixed ether solvent containing an aromatic ether solvent and an aliphatic ether solvent.
  • the mixed ether solvent may be well mixed with the alcohol solvent, and may be uniformly dispersed by dissolving the added epoxy resin for imparting adhesion. Therefore, the metal nanoparticles to which the primary amine ligand is bound or adsorbed may be dispersed by a nonpolar organic solvent, thereby improving compatibility with the epoxy resin by the mixed ether solvent.
  • the metal nanoparticles may be bonded to the surface of the substrate through an epoxy resin, thereby improving adhesion between the substrate and the circuit pattern.
  • the metal nanoparticles decrease in size as the carbon number of the carboxylate ligands and the primary amine ligands bonded or adsorbed on the surface decreases in size, and thus has a property of a nonpolar material. It can be uniformly dispersed, thus improving compatibility with the epoxy resin and improving the double dispersion stability, thereby forming a uniform thin film circuit pattern on the substrate.
  • dispersibility of the epoxy resin may be lowered when using a hydrocarbon solvent such as roluene or xylene as the nonpolar organic solvent.
  • the present invention includes a mixed ether solvent containing an aromatic ether solvent and an aliphatic ether solvent to disperse the metal nanoparticles and at the same time to disperse the epoxy resin, and to further improve their dispersion stability It includes.
  • a metal ink composition to form a surface-treated thin film circuit pattern having excellent adhesion properties to the substrate without the step of the substrate, while maintaining the dispersion stability (a) (: ⁇ ( : 20-carboxylic Metal nanoparticles capped by a carboxylate ligand and a C 5 to C 20 primary amine ligand; (b) apolar organic solvent; (c) epoxy resin; (d) curing agent; (e) aromatic ether solvent and A mixed ether solvent containing an aliphatic ether solvent, and (f) a dispersant.
  • the low viscosity metal ink composition of the present invention comprises metal nanoparticles.
  • the metal nanoparticles are capped by a carboxylate ligand of C ⁇ C 20 and a primary amine ligand of C 5 to C 20 .
  • the metal nanoparticles include a metal core, (: ⁇ (: 20 carboxylate ligand, and C 5 ⁇ C 20 primary amine ligand, the carboxylate ligand and primary amine
  • the ligands are bound to or adsorbed to the surface of the metal core, respectively.Since these metal nanoparticles are nano-sized, the ratio of surface atoms to total atoms is greatly increased compared to bulk metals, which results in unstable nanoparticles.
  • the melting point is lowered, and thus, even in low-temperature firing, secondary recombination between metals forms particles to form grains and grain boundaries.
  • the contact area with the substrate is increased to form a thin film circuit pattern having excellent conductivity and adhesion to the polymer substrate.
  • the metal nanoparticle may be an aromatic ether solvent and an aliphatic ether. Since it is excellent in compatibility with an epoxy resin by heunhap ether-based solvent containing a solvent, it is possible to implement a thin film circuit pattern excellent in adhesion to a substrate by an epoxy resin.
  • metal nanoparticles are not particularly limited, and for example, nanoparticles of a metal selected from the group consisting of Groups 1 to 14 on the periodic table, preferably gold, silver, copper, nickel, platinum, cobalt, and paralysis.
  • nanoparticles such as aluminum, tin, zinc, iron, indium, magnesium, and more preferably silver nanoparticles. These may be used alone or in combination of two or more thereof.
  • Such metal nanoparticles are capped by a carboxylate ligand of (: ⁇ (: 20) and a primary amine ligand of C 5 -C 20 .
  • the carboxylate ligand of C ⁇ C 20 is a capping ligand having a structure of R-C00— (wherein R is a saturated or unsaturated aliphatic hydrocarbon group of (: ⁇ (: 20 , preferably C 8 ⁇ C 15). Saturated or unsaturated aliphatic hydrocarbon group), it is possible to improve the dispersion stability of the metal nanoparticles by preventing puncture between the particles, and the size of the metal nanoparticles are adjusted according to the type of the carboxylate-based ligand thin film In particular, as the carbon number of the carboxylate ligand increases, the particle size is controlled to be smaller, so that the firing can be performed at a low temperature of about 200 to 250 ° C.
  • a thin film circuit pattern having high adhesion and conductivity to a polymer substrate may be implemented.
  • Oxtanonate ligand, nonanoate ligand, decanoate ligand, dodecanoate ligand, oleate ligand, and the like but are not limited thereto.
  • the primary amine ligand is a capping ligand having a structure of C n H 2n + 1 N3 ⁇ 4 (wherein n is from 5 to 20, preferably from 10 to 18), preventing coarsening between particles, and increasing solubility of the metal.
  • compatibility between the metal nanoparticles and the epoxy resin may be improved.
  • the amine-based ligand may promote curing of the epoxy resin, which may later affect the heat treatment temperature of the metal ink composition coated on the substrate.
  • Examples of such primary amine ligands include, but are not particularly limited to, octylamine ligand, decylamine ligand, dodecylamine ligand, oleylamine ligand, and the like.
  • the average particle diameter of the metal nanoparticles capped by these ligands is not particularly limited.
  • the size of the metal nanoparticles is about 20 nm or less, preferably about 2 to 20 kPa, the melting silver becomes low due to the size effect of the nanoparticles, so that the particles melt even at a low temperature of about 200 ° C.
  • secondary recombination between metals is induced, thereby realizing high conductivity and simultaneously increasing contact area with the substrate through recombination of metals connected between particles, thereby achieving high adhesion.
  • the content of the metal nanoparticles is not particularly limited, and adjusted in consideration of the thickness of the thin film circuit pattern to be formed. However, in the present invention, as the content of the metal nanoparticles increases, the content of the epoxy resin also increases to increase the> viscosity of the metal ink composition. Thus, when the content of the metal nanoparticles is about 30 to 80% by weight, preferably about 40 to 60% by weight, based on the total weight of the metal ink composition, the viscosity of the metal ink composition may be as low as about 5 to 500 cps.
  • Such metal nanoparticles can be prepared by various methods.
  • the metal nanoparticles produced in the step S300 may further include a step of immersing and washing with alcohol in alcohol.
  • a compound having the structure of carboxylic acid of CrCzo be used in the present invention is R-C00H (where R is (: ⁇ (: waiting for a saturated or unsaturated aliphatic hydrocarbon group of 20), for example, caprylic acid (capryl ic acid), Pella Pelargonic acid, capric acid, lauric acid, oleic acid, and the like, but are not limited thereto.
  • the carboxylic acid of d to C 20 may be a carboxylic acid solution obtained by dissolving in a first solvent (: ⁇ (: 20.
  • the first solvent usable may be It will not restrict
  • Non-limiting examples of the first solvent is water, methanol, ethanol, propane, 'isopropanol, butanol, pentane, hexane, dimethylsulfoxide (dimethyl sulphoxide, DMS0), ⁇ , ⁇ - is methyl formamide (N , N-dimethyHormamide (DMF), ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol, propylene glycol propyl ether, propylene glycol methyl ether acetate, N- N-methyl pyrrol idone, methyl isobutyl ketone, methyl ethyl ketone, acetonitrile, tetrahydrofuran (THF), hexadecane ), Pentadecane, tetradecane, tridecane, dodecane, undecane, decane, decane, nonane, oct
  • the carboxylate of d-o is not particularly limited as long as it is obtained by reacting the carboxylic acid of (: ⁇ (: 20 ) with a base or reacting the carboxylic acid with a solution obtained by dissolving the carboxylic acid in a second solvent.
  • the base can easily bind metal ions of a metal salt to hydrogen sites of the carboxylic acid, thereby easily obtaining a metal carboxylate, for example, when decanoic acid is reacted with sodium hydroxide as a base, decanoic acid.
  • Examples of the base are not particularly limited, and for example, NaOH, NH 4 0H, There are like NaHCOs, Na 2 C0 3, KOH , Ga (0H) 2, Ba (0H) 2, Mg (0H) 2, K 2 C0 3, KHC0 3, CaC0 3, not limited to this.
  • decanoic acid can be reacted with sodium hydroxide.
  • sodium hydroxide may be added to decanoic acid in the same molar ratio because the carboxyl group of decanoic acid and sodium ions of sodium hydroxide react with 1: 1.
  • An example of the second solvent for dissolving the base is not particularly limited as long as it is a solvent commonly used in the art, and is the same as the example of the first solvent described above, preferably water.
  • Metal salts that can be used in the present invention is not particularly limited, for example, inorganic salts of metals selected from the group consisting of Groups 1 to 14 on the periodic table, preferably gold, silver, copper, nickel, platinum, cobalt, palladium, Inorganic salts such as aluminum, tin, zinc, iron, indium, magnesium, and the like, and more preferably, inorganic salts of silver and the like, which are used alone or in combination of two or more thereof.
  • the inorganic salts are nitrates, sulfates, acetates, phosphates, silicates, hydrochlorides and the like.
  • This metal salt may be in a solution state obtained by dissolving in a third solvent.
  • examples of the three solvents that can be used are not particularly limited as long as they are commonly used in the art, and are the same as the examples of the first solvent described above, and preferably water.
  • the metal salt and the ( ⁇ ⁇ (:. A carboxylic acid or salt heunhap the ratio of the 20 may be heunhap in various amounts depending on the type of carboxylic acid or its salt type or a metal salt is used, however, the ( ⁇ (20 carboxylic acid or In salt When the metal salt is added, a slurry is generated. At this time, when the molar concentration of the carboxylic acid is higher than the amount of the organic solvent or water used, the amount of metal carboxylate produced is increased and the viscosity is increased, so that the reaction does not occur smoothly.
  • step S100 in order to remove uncoated water or water from the selectively produced Cr ⁇ C 20 metal carboxylate, after the reaction is finished, the metal carboxylate of d-Co produced in step S100 after washing with water, alcohol (eg , Methanol) can be filtered and washed, and then dried in a vacuum oven at about 40-50 ° C.
  • alcohol eg , Methanol
  • step S200 is a step of reacting the metal carboxylate of d-Cso generated in step S100 with the primary amine of C 5 to C 20.
  • oleylamine when Ag-carboxylate [C3 ⁇ 4 (CH 2 ) 8 -C00—Ag + ] reacts with oleylaraine, oleylamine is used as a ligand to form Ag-carboxylate. As shown in the following formula (1) by coordinating with silver ions, it is possible to obtain an Ag-carboxylate complex to which oleylamine is bound.
  • the primary amine of C 5 ⁇ C 20 serves as a solvent to increase the dissociation degree of the metal carboxylate of the d-Co, and is coordinated to the metal ions of the metal carboxylate, and subsequently metal nanoparticles in the conductive ink composition It serves to improve the compatibility between the particles and the epoxy resin.
  • the primary amine may later affect the heat treatment temperature of the metal ink composition.
  • the primary amine that can be used is not particularly limited as long as it can react with dissociating metal carboxylate of (: ⁇ (: 20) , but a compound having a structure of C n 3 ⁇ 4 n + 1 N3 ⁇ 4 (wherein n is 5 to 20, In the case of 10 to 18, the dispersion stability of the metal nanoparticles in the metal ink composition and the adhesion property of the thin film circuit pattern are improved, and the printed ink composition is heat-treated at low silver so as to obtain a uniform fine thin film circuit pattern.
  • Specific examples include, but are not limited to octylamine, decylamine, dodecylamine, and oleylamine.
  • the aforementioned - (: Primary heunhap ratio of the amines of 20 metal of the carboxylic acid salt and a C 5 ⁇ C 20 is not particularly limited, one or two: If a molar ratio of 1.8 to 3, by increasing the metal carboxylate yeomkkoe dissociation The binding of the metal carboxylate and the primary amine can be promoted.
  • step S300 the primary amine of C 5 to C 20 obtained in step S200 is A reducing agent is added to the combined metal carboxylate complex of ⁇ (: 20 to form metal nanoparticles.
  • the reducing agent is added to the metal carboxylate complex of d-o to which the primary amine of C 5 to C 20 is bonded,
  • the metal ions of the metal carboxylate complex are reduced to -metal atoms to form metal particles, except that the formed metal particles are condensed with each other due to surface instability to form a globule, but are bonded to the metal ions of the complex.
  • the primary amines of C 5 to C 20 and the carboxylates of C ⁇ c 20 are bonded or adsorbed on the surface of the metal particles to block aggregation between the metal particles, thereby dispersing the metal particles to form nano-sized metal particles.
  • the reducing agent usable in the present invention is not particularly limited, and non-limiting examples include hydrogen compounds such as hydrogen, hydrogen iodide, hydrogen sulfide and aluminum hydride; Lower oxides such as carbon monoxide and sulfur dioxide; Lower oxygen acid salts such as sulfite and sodium sulfide; The electrically-positive large cations such as alkali metals, magnesium and zinc.
  • Prone metal Organic compounds having a low degree of oxidation such as aldehyde, sugar oil, formic acid, oxalic acid, amine compounds such as hydrazine, phenylhydrazine and 1-amino-4-methyl piperazine, and the like, preferably hydrazine, phenylhydrazine and 1-amino Amine compounds such as 4-methyl piperazine. These may be used alone or in combination of two or more thereof.
  • the content of such a reducing agent is not particularly limited, and is adjusted in consideration of the size and yield of the metal nanoparticles. However, when the content of the reducing agent is about 1 to 1.2 equivalent ratio based on the metal in the metal carboxylate complex, while the yield of the metal nanoparticles is improved, the size of the metal nanoparticles can be adjusted to about 2 to 8 ran. have.
  • optionally immersed in alcohol to wash the metal nanoparticles produced in step S300, and may further comprise the step of filtering. When the metal nanoparticles of step S300 are immersed in alcohol, the metal nanoparticles may be precipitated while the remaining amine compound, carboxylic acid, and reducing agent are removed. Thereafter, the precipitated metal nanoparticles may be obtained through a filtration process such as centrifugation.
  • the metal nanoparticles prepared as described above are mixed with the components of the ink composition below and not dried. If the dried metal nanoparticles are mixed with the following components, spacing between the metal nanoparticles may occur, which may lower dispersion stability of the ink composition, and thus, it may be difficult to obtain a high concentration of conductive ink.
  • the low viscosity metal ink composition of the present invention comprises a nonpolar organic solvent.
  • the nonpolar organic solvent may improve the dispersion stability of the ink composition when the metal nanoparticles are dispersed, and may further control the viscosity of the ink composition.
  • nonpolar organic solvents include hydrocarbon solvents having 5 to 20 carbon atoms, or high boiling alcohol solvents having boiling points of 6 to 15 carbon atoms (boiling points of about 150 ° C. or more), but are not limited thereto.
  • the high-boiling alcohol-based solvent has a molecular weight increases as the carbon number is 6 to 15, so that the solubility in water is lowered to exhibit a nonpolar nature.
  • non-limiting examples of the hydrocarbon solvent having 5 to 20 carbon atoms include toluene, xylene, nucleic acid, tetradecane, octadecene and the like, and the high boiling point alcohol solvent having 6 to 15 carbon atoms.
  • Non-limiting examples include heptane, octane, 2-ethyl-1-nucleic acid, decane, dodecanol, and the like, with octane or 2-ethyl-1-nucleic acid being preferred. More than one species may be used in combination.
  • the content of the nonpolar organic solvent is not particularly limited, and is a residual amount adjusted so that the total amount of the ink composition is 100 weight 3 ⁇ 4.
  • the low viscosity metal ink composition of the present invention has the following aromatic ether solvents and aliphatic ether solvents capable of dispersing the epoxy resin together with a nonpolar organic solvent. It includes a mixed ether solvent containing.
  • the dispersion stability of the metal nanoparticles and the epoxy resin is improved, since the viscosity of the metal ink composition is adjusted to 5 to 500 cps, the low viscosity metal ink composition of the present invention is ink-jet printing or ink-jet printing. Can be applied to rolI-to-roU printing.
  • the low viscosity metal ink composition of the present invention comprises an epoxy resin.
  • the epoxy resin is a binder resin, excellent compatibility with the metal nanoparticles serves to improve the adhesion between the thin film circuit pattern and the engine.
  • Examples of the epoxy resin can be used without limitation as long as it is a conventional epoxy resin known in the art, it is preferable that two or more epoxy groups are present in one molecule.
  • Non-limiting examples of usable epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, novolac epoxy resins, flame retardant epoxy resins, flame retardant epoxy resins and cycloaliphatic epoxy resins. , Rubber modified epoxy resin, alkylphenol novolak type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthol type epoxy resin, dicyclopentadiene type epoxy resin, etc. It may be used alone or in combination of two or more.
  • More specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, biphenyl type epoxy resins, tetramethyl biphenyl type epoxy resins, and phenol furnaces.
  • the above-mentioned epoxy resins may be used alone or in combination of two or more thereof.
  • the epoxy equivalent of the said epoxy resin is not specifically limited, In order to further improve the adhesive characteristic of a board
  • the content of the epoxy resin is not particularly limited, and a low viscosity when from about 40 to 80% by weight, based on the total weight of the metallic ink composition, as well as improving the adhesive property of the thin film circuit pattern and the substrate, from about 5 to about 3.2E- It is desirable to realize thin film circuit patterns with specific resistance as low as 5.2E— 5 ⁇ -cm.
  • the low viscosity metal ink composition according to the present invention comprises a curing agent.
  • the curing agent may be used without limitation as long as it is a conventional curing agent known in the art that the epoxy resin and the curing reaction can proceed, and may be appropriately selected according to the type of epoxy resin to be used.
  • the curing agent examples include amines, aliphatic amines, modified aliphatic amines, amine-based curing agents such as aromatic amines, acid anhydride curing agents, and polyamides.
  • Resins Polyamide
  • Polysulfide resin Polysulfide
  • amine complex Amin Com lex
  • phenol resin Phenol
  • dicyyanamide Dicyanamide
  • the content of such a curing agent is not particularly limited and may be appropriately adjusted according to the content of the epoxy resin.
  • the content of the curing agent may be about 0.1 to 3% by weight based on the total weight of the metal ink composition.
  • the low viscosity metal ink composition according to the present invention includes an ether solvent (hereinafter, 'a mixed ether solvent') in which an aromatic ether solvent and an aliphatic ether solvent are mixed.
  • the mixed ether solvent may disperse the metal nanoparticles and at the same time disperse the epoxy resin to improve dispersion stability of the ink composition and further control the viscosity of the ink composition.
  • Non-limiting examples of the aromatic ether solvent include an aromatic ether solvent containing an alkoxy group of d-Cs, and specific examples thereof include methoxybenzene (Anisole), but are not limited thereto.
  • non-limiting examples of the aliphatic ether solvent include an aliphatic ether solvent containing an alkoxy group of d ⁇ C 6 , specific examples are diethylene glycol monobutyl ether acetate (BCA), dimethyl Ether, diethyl ether, dibutyl ether, dipropyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, and the like, but are not limited thereto.
  • the content of the mixed ether solvent is not particularly limited, when the content is about 20 to 25% by weight based on the total weight of the metal ink composition, the dispersibility of the epoxy resin is further improved, and the viscosity of the ink composition is about 5 to 500. cps can be adjusted.
  • the mixing ratio of the aromatic ether solvent and the aliphatic ether solvent is not particularly limited, but in the case of 6 to 8: 4 to 2 weight ratio, both dispersibility of the metal nanoparticles and the epoxy resin is further improved to Dispersion stability can be further improved.
  • the low viscosity metal ink composition according to the present invention comprises a dispersant.
  • the dispersant By including the dispersant, the dispersion stability of the metal nanoparticles and the epoxy resin may be improved to form a uniform thin film circuit pattern. Further, the dispersant may enhance the ink composition of / storage stability by preventing the agglomeration among the metal nanoparticles during storage of the metallic ink composition.
  • Examples of the dispersant may be any conventional dispersant known in the art without limitation, and examples thereof include a polymer or low molecular weight wet dispersant, and include fatty acid or phosphate ester compounds, and specifically, DISPERBYK-110 and DISPERBYK-111. And phosphate ester compounds such as DISPERBYK-102.
  • the content of the dispersant is not particularly limited, but when the metal ink composition is about 1 to 5 weight 3 ⁇ 4, dispersion stability and storage stability of the metal nanoparticles may be further improved.
  • the low viscosity metal ink composition of the present invention may optionally further comprise a curing accelerator.
  • the curing accelerator is not particularly limited as long as it is a substance capable of appropriately controlling the curing rate of the epoxy resin or a substance capable of controlling the rate of the curing agent.
  • curing accelerators may include imidazole-based curing accelerators and derivatives thereof.
  • Non-limiting examples of the above imidazole series curing accelerators include 1-methyl imidazole, 2-methyl imidazole, 2-ethyl imidazole, 2-decylimidazole, 2 ′ nucleotylimidazole and 2-iso.
  • the content of the curing accelerator is not particularly limited, but may be included in the range of about 0.01 to 10% by weight based on the total weight of the metal ink composition, preferably may be included in the range of about 0.01 to 5 weight 3 ⁇ 4, more preferably Preferably in the range of about 0.01 to 0.5% by weight.
  • curing of the ink composition can be performed at a low temperature for a short time, and the integrity of the ink composition is good.
  • the low viscosity metal ink composition of the present invention can be prepared through various methods.
  • metal nanoparticles capped by a carboxylate ligand of ⁇ (: 20) and a primary amine ligand of C 5 ⁇ C 20 , an apolar organic solvent, an epoxy resin, a curing agent, an ether organic solvent It may be prepared by mixing and dispersing the dispersing agent, but when the metal nanoparticles are in a dried state, agglomeration between particles may occur and the dispersion stability may be lowered, resulting in high concentration of the metal nanoparticles. Because of the difficulty, the metal nanoparticles are preferably mixed in a non-dried state.
  • the metal ink composition of the present invention described above is heat-treated after being printed on a substrate without a surface treatment process of the substrate, thereby realizing a fine thin film circuit pattern having excellent adhesive properties and high conductivity with the substrate.
  • the metal ink composition printed on the substrate may improve the adhesion between the substrate and the thin film circuit pattern formed on the substrate due to the curing of the epoxy resin and at the same time the melt and secondary recombination between the metal nanoparticles during heat treatment.
  • the temperature during the heat treatment is adjusted in consideration of the thermal decomposition temperature of the primary amine capping the metal nanoparticles and the curing conditions of the epoxy resin, it is preferable to adjust the temperature range to the melting and secondary recombination of the metal nanoparticles. Do.
  • the heat treatment temperature is about 200 to 250 ° C
  • the size of crystal grains generated due to melting and secondary recombination of the metal nanoparticles is increased to increase the contact area with the substrate, thereby curing the epoxy resin substrate
  • the adhesive property between the thin film circuit pattern can be further improved.
  • the adhesion of the circuit pattern to the substrate may be 5B or more in the cross-cut test according to ASTM D 3359.
  • the low viscosity metal ink composition of the present invention may be fired at a low temperature.
  • the metal ink composition can be applied to organs of various materials.
  • substrates that can be used include glass substrates and polymer substrates, but are not limited thereto.
  • the metal ink composition can be applied to a polyimide (PI) substrate material.
  • PI polyimide
  • the viscosity of the metal ink composition may be adjusted according to the type of epoxy resin, the amount of the nonpolar organic solvent and the ether solvent, and may be, for example, about 5 to 500 cps. According to an example of the present invention, when the metal ink composition is used for inkjet printing, the viscosity of the composition may be adjusted to about 5 to 15 cps.
  • the metal ink composition may be formed through a roll-to-roll process such as micro gravure, a slot die, or a coating process such as inkjet, and then subjected to a heat treatment of about 200 to 250 ° C. While maintaining adhesion to polyimide substrates of at least 5B in cross-cut tests according to ASTM D 3359 A thin film circuit pattern having a specific resistance of about 3.2E— 5 to 5.2E 5 ⁇ ⁇ cm may be formed.
  • the present invention provides a printed circuit board manufactured using the low viscosity metal ink composition described above. In this case, the low-viscosity metal ink composition forms a circuit layer on the substrate, the circuit layer is excellent in adhesion to the substrate, and has high electrical conductivity.
  • the method of forming a circuit layer with the said metal ink composition is not specifically limited.
  • a roll-to-roll process such as micro gravure and slot die, a screen method, inkjet printing, spray coating, and the like, but are not limited thereto.
  • the forming initial condition is adjusted according to the conditions known in the art.
  • the low-viscosity ink composition may be formed on the polyimide substrate through a microgravure coating or finely coated on the polyimide substrate, and then heat-treated at about 200 to 250 ° C. to form a circuit layer on the substrate. have.
  • the substrate usable in the present invention is not particularly limited as long as it is a substrate known in the art, and as described above, the low-viscosity metal ink composition can be fired at a low temperature, so that not only a glass substrate but also a polyimide (PI) and a PEN film Polymer substrates such as these may also be used.
  • PI polyimide
  • PEN film Polymer substrates such as these may also be used.
  • the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following Examples, Comparative Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
  • the third solution was slowly added dropwise to the formed sodium octanoate to obtain a suspension in which silver octanoate as a white precipitate was produced. Subsequently, the suspension was filtered under reduced pressure and filtered with primary washing with purified water, and the resulting solution was filtered under reduced pressure and filtered with secondary washing with methane, and dried in a convention oven at 40 to 50 ° C. to obtain white silver octanoic acid.
  • a metal nanoparticle was obtained in the same manner as in Preparation Example 1, except that dodecylamine was used instead of octylamine used in preparing the metal nanoparticle of Preparation Example 1.
  • the metal nanoparticles obtained at the time are silver nanoparticles (hereinafter, 'silver nanoparticles B') capped by octanoate ligands and dodecylamine ligands. Its size (particle diameter) was about 5-15 nm.
  • the obtained metal nanoparticles were silver nanoparticles (hereinafter referred to as 'silver nanoparticles C') capped by octanoate ligands and oleylamine ligands, and their size (particle diameter) was about 3 to 8 nm. .
  • Preparation Example 1 is set as follows: Preparation Example 1, except that the octanoic acid used in place of the metal precursor prepared using the acid 139.6g (0.5mol), to obtain the metal nanoparticles.
  • the metal nanoparticles obtained at this time were silver nanoparticles (hereinafter, 'silver nanoparticles D') capped by decanoate ligand and octylamine ligand, and their size (particle diameter) was about 3 to 10 run.
  • Example 1 (0.5 mol) was used, except that dodecylamine was used instead of octylamine used in preparing the metal nanoparticles of Preparation Example 1, the metal nanoparticles were obtained in the same manner as in Example 1.
  • nanoparticles are decanoate ligand and dodecylamine
  • nanoparticle is E '
  • its size was about 3 ⁇ 7 nm.
  • the obtained metal nanoparticle ' is a silver nanoparticle (hereinafter,' silver nanoparticle F ') capped by a decanoate ligand and an oleylamine ligand, and its size (particle size) was about 3 to 3.5 nm. -
  • Example 2 A low viscosity metal ink composition was obtained in the same manner as in Example 1 except for using the silver nanoparticles E prepared in Preparation Example 5 instead of the silver nanoparticles C used in Example 1.
  • Silver Nanoparticle C Used in Example 1 Mass Production A low-viscosity metal ink composition was obtained in the same manner as in Example except that silver nanoparticle F prepared in Preparation Example 6 was used. ⁇ Example 4>
  • a low viscosity metal ink composition was obtained in the same manner as in Example 1 except that the silver nanoparticles A prepared in Preparation Example 1 were used instead of the silver nanoparticles C used in Example 1.
  • a low viscosity metal ink composition was obtained in the same manner as in Example 1 except that the silver nanoparticles B prepared in Preparation Example 2 were used instead of the silver nanoparticles C used in Example 1. -
  • a low viscosity metal ink composition was obtained in the same manner as in Example 1 except for using the silver nanoparticles D prepared in Preparation Example 4 instead of the silver nanoparticles C used in Example 1. Comparative Example 1
  • Each of the low viscosity metal ink compositions of Examples 1 to 6 were subjected to a pattern or front coating on the plyimide film through microgravure coating, respectively, under the following coating conditions, and then heat-treated at 200 to 25 CTC.
  • the low-viscosity metal ink composition according to the present invention easily formed a fine thin film circuit pattern on the polyimide film, and was also easily coated with a uniform thickness upon front coating on the polyimide film.
  • Each metal ink composition was left for 4 weeks in phase silver to check the occurrence of precipitates such as metal nanoparticles and epoxy binders to evaluate dispersion stability. At this time, it was evaluated as follows according to the generation time of the precipitate. ⁇ : more than 4 weeks ,
  • Adhesion was evaluated by repeating the cross-cut tape test five times in accordance with ASTM D 3359. Here, when measuring the adhesion, it was measured after coating each ink composition on a polyimide film as in the coating experiment.
  • the specific resistance ( ⁇ ⁇ ⁇ ) was calculated according to the following equation (1).
  • the specific resistance as measured in the coating property test as described below after coating each ink composition on a polyimide film.
  • Comparative Example 1 containing no epoxy resin and a dispersing agent, the dispersion stability was excellent, but the adhesive strength was very low because a binder that could impart adhesion to the substrate was not included.
  • Comparative Example 2 which does not contain a mixed ether solvent, the dispersion of the epoxy resin was not secured and precipitated immediately, and thus the adhesive force and the specific resistance could not be measured.
  • Comparative Example 3 containing no dispersant, although the adhesive strength was high and the specific resistance was low, dispersion stability was not secured during long time storage.
  • Comparative Example 4 containing silver particles, the specific resistance was low, but the adhesive force was very low because a binder that could impart adhesion to the substrate was not included.
  • the silver nanoparticles when included together with the epoxy resin according to the present invention, when the silver nanoparticles include a mixed ether-based solvent capable of dispersing the silver nanoparticles and the epoxy resin and a dispersant which may improve storage stability, As dispersion stability is improved, a thin film circuit pattern with high adhesion and electrical conductivity to a substrate can be realized. I knew you could.
  • the metal ink composition of Example 2 includes silver nanoparticles capped by the decanoate ligand, and more than the metal ink composition of Example 5 (including silver nanoparticles capped by the octanoate ligand). Dispersion stability was excellent. However, in Example 6, silver nanoparticles were capped by the decanoate ligand as in Examples 2 and 3, but dispersion stability was somewhat lower than in Examples 1 to 3 as in Example 4. From these results, it can be seen that not only the carbon number of the carboxylate ligand capping the metal nanoparticles, but also the coarsening of the metal nanoparticles in the metal ink composition can be controlled according to the carbon number of the primary amine.
  • a carbolate ligand : 20
  • a primary amine ligand of C 5 -C 20 preferably a carbock of C 8 — C 15
  • the type and content of silver nanoparticles (Ag nano particles, Ag NP), the content of 2-ethyl-1-nucleic acid, the content of the epoxy resin, the content of the curing agent, except for adjusting the content of the curing accelerator, the content of the BCA, and the content of the dispersant, it was carried out in the same manner as in Example 1 to obtain a low viscosity metal ink composition of Examples 7 to 12.

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  • Life Sciences & Earth Sciences (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

La présente invention concerne une composition d'encre métallique et une carte de circuits imprimés l'utilisant, la composition d'encre métallique pouvant former un motif de circuit de film mince ayant une excellente propriété d'adhérence à un substrat et une conductivité élevée sans effectuer un procédé de traitement de surface sur le substrat.
PCT/KR2013/012164 2012-12-26 2013-12-26 Composition d'encre métallique à faible viscosité, et carte de circuits imprimés l'utilisant WO2014104737A1 (fr)

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KR10-2012-0153780 2012-12-26
KR1020120153780A KR101547622B1 (ko) 2012-12-26 2012-12-26 저점도 금속 잉크 조성물 및 이를 이용하는 인쇄회로기판

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KR102493082B1 (ko) * 2017-11-28 2023-02-01 삼성디스플레이 주식회사 잉크 조성물, 이의 제조 방법 및 이를 이용한 윈도우 부재의 제조 방법
KR102266732B1 (ko) * 2020-03-05 2021-06-21 엔젯 주식회사 전도성 잉크 조성물

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2010138281A (ja) * 2008-12-11 2010-06-24 Kansai Paint Co Ltd カチオン電着塗料及び塗装物品
KR20110021681A (ko) * 2009-08-26 2011-03-04 주식회사 엘지화학 전도성 금속 잉크 조성물 및 전도성 패턴의 형성 방법
KR20120096499A (ko) * 2009-11-09 2012-08-30 카네기 멜론 유니버시티 금속 잉크 조성물, 전도성 패턴, 방법, 및 장치

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010138281A (ja) * 2008-12-11 2010-06-24 Kansai Paint Co Ltd カチオン電着塗料及び塗装物品
KR20110021681A (ko) * 2009-08-26 2011-03-04 주식회사 엘지화학 전도성 금속 잉크 조성물 및 전도성 패턴의 형성 방법
KR20120096499A (ko) * 2009-11-09 2012-08-30 카네기 멜론 유니버시티 금속 잉크 조성물, 전도성 패턴, 방법, 및 장치

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