KR100727434B1 - Transparent silver ink composition and thin film formation method using the same - Google Patents

Abstract

The present invention provides a silver complex compound obtained by reacting at least one silver compound represented by Formula 1 with at least one ammonium carbamate or ammonium carbonate compound represented by Formula 2, Formula 3, or Formula 4, and an amine compound, Formula 2, Formula The present invention relates to a transparent silver ink composition comprising a compound of Formula 3 or Formula 4 or at least one or more of these mixtures, a method for preparing the same, and a method for forming a thin film using the same.

   (Formula 1)

  (Formula 2)

 (Formula 3)

 (Formula 4)

Silver Complex Compound, Stabilizer, Silver Ink, Thin Film, Patterning

Description

 Transparent silver ink composition and thin film formation method using the same {TRANSPARENT SILVER INKS AND THEIR METHODS FOR FORMING THIN LAYERS}

1 is a TGA thermogram of the silver ink composition of Example 2;

FIG. 2 is a diagram output using the ink jet printer of Example 32

 (A): PET film, (B): imide film, (C): glass plate

FIG. 3 shows a PET film using the silk screen printing machine of Example 33.

Printed Drawing

4 is a PET film using the gravure printing machine of Example 34.

       Printed Drawing

The present invention provides a transparent silver ink composition comprising a silver complex compound having a special structure and a stabilizer for stabilizing the complex compound, and a thin film forming method using the same.

Ullmann's Encyclopedia of Ind. Chem. , Vol. In A24, 107 (1993), silver is a precious metal that is not easily oxidized, has excellent electrical and thermal conductivity, and has a catalytic and antibacterial effect. Therefore, silver and silver compounds are used in alloys, plating, medicine, photography, electrical and electronics, It is widely used in industries such as textiles, detergents and home appliances. In addition, silver compounds can be used as catalysts for the synthesis of organic materials and polymers, and in particular, the use of lead in electrical and electronic component circuits, low resistance metallization, printed circuit boards (PCB), flexible printed circuit boards (FPC), and wireless recognition ( RFID pattern antennas, electromagnetic shielding and metal patterns in new fields such as plasma displays (PDPs), liquid crystal displays (TFT-LCDs), organic light emitting diodes (OLEDs), flexible displays and organic thin film transistors (OTFTs). There is a growing interest in silver, which is needed or used as an electrode.

When silver is used, most of it is made of nano particles or powder, silver paste on flake and silver paste containing binder resin or solvent and used directly or silver compound such as silver nitrate is reacted with other compounds in aqueous solution or organic solvent to collect colloid or fine particles. It forms and uses various forms of silver and organic silver compounds. Such organic silver compounds are used to form metal patterns by various methods such as chemical vapor deposition (CVD), plasma deposition, sputtering, electroplating, photolithography, electron beams, and lasers.

Among the organic silver compounds, the most commonly known ligands of Organic Silver Complexes are carboxylic acids ( Prog. Inorg. Chem., 10 , p233 (1968)). Light sensitive, low solubility in organic solvents ( J. Chem. Soc., (A)., P514 (1971), US Patent No. 5,534,312 (July 9, 1996)) Despite its ease, there are limitations to the application. To solve this problem, J. Inorg. Nucl. Chem. , 40, p 1599 (1978), Ang. Chem., Int. Ed. Engl. , 31, p 770 (1992), Eur. J. Solid State Inorg. Chem. , 32, p 25 (1995), J. Chem. Cryst. , 26, p99 (1996), Chem. Vapor Deposition , 7, 111 (2001), Chem. Mater. , 16, 2021 (2004), U.S. Patent No. 5,705,661 (January 6, 1998), and Korean Patent Publication No. 2003-0085357 (Nov. 5, 2003). And a method of using a compound having a long alkyl chain in an acid or including an amine compound or a phosphine compound. However, until now, derivatives of compounds derived from silver are limited, and furthermore, they have a disadvantage in that the decomposition temperature is high and the decomposition rate is slow to form a pattern with metals, which lack stability and solubility.

The present inventors also present a silver complex compound having a stable and excellent solubility and a method for producing the same as in Korean Patent Application Nos. 2005-11475 and 2005-11478, but using a metal pattern as described above for various applications Highly successful ink compositions are required for successful manufacture.

Accordingly, the present inventors have successfully reached the present invention as a result of diligent efforts to solve these problems. That is, the present invention has excellent stability and solubility through continuous experiments, so that the thin film is easily formed, and is easily baked even at a low temperature of 150 ° C. or lower, and thus uniform and dense thin film or pattern is formed while having high conductivity regardless of the type of substrate. It is possible to provide a transparent silver ink composition and a method for manufacturing the same, which can be applied to various applications using the same.

SUMMARY OF THE INVENTION An object of the present invention is to provide a transparent silver ink composition comprising a silver complex compound having a special structure and an amine compound or a stabilizer of a compound of formula (2), (3) or (4) or at least one or more of these mixtures, and a method for preparing the same. will be.

Still another object of the present invention is to provide a transparent silver ink composition excellent in stability and solubility and easy to form a thin film regardless of the type of substrate, and a method of manufacturing the same.

It is still another object of the present invention to provide a transparent silver ink composition which is easily calcined even at a low temperature of 150 ° C. or less, and which is easy to form a uniform and dense silver thin film or pattern having high conductivity, and a method of manufacturing the same.

In order to achieve the above object, the present inventors have conducted a number of studies and react one or more silver compounds represented by the following Chemical Formula 1 with one or more ammonium carbamate or ammonium carbonate-based compounds represented by Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4; The present invention has been invented a transparent silver ink composition comprising a silver complex compound and a stabilizer which is an amine compound, a compound of formula (2), (3) or (4) or at least one of these mixtures, and a method for preparing the same.

(Formula 1)

(Formula 2)

(Formula 3)

(Formula 4)

In Formula 1, n is an integer of 1 to 4, X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, Specific examples of tetrafluoroborate, acetylacetonate, carboxylate and the like include silver oxide, thiocyanated silver, silver sulfide, silver chloride, silver cyanide, silver cyanated silver, silver carbonate, silver nitrate, silver nitrite Silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoroborate, silver acetylacetonated silver, silver acetate, silver lactate, silver oxalate and derivatives thereof, and the like, but are not particularly limited thereto. The use of silver or silver carbonate is more preferred in terms of reactivity and post-treatment.

And in Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R 6 may be the same as or different from each other, and are each hydrogen, aliphatic or cycloaliphatic having 1 to 30 carbon atoms. And an alkyl group or an aryl or an aralkyl group which is a mixture thereof, an alkyl and aryl group substituted with a functional group, and a group consisting of a heterocyclic compound, a polymer compound and derivatives thereof, but is not particularly limited thereto. Specifically, for example, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, doco Decyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxy propyl, methoxypropyl, cyanoethyl, ethoxy, butoxy, hexyloxy , Methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, pyrrole, imidazole, pyridine, Carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and derivatives thereof, and high molecular compounds such as polyallylamine or polyethyleneimine and derivatives thereof Like This is not particularly limited. Specific examples of the compound include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethyl carbamate, isopropylammonium isopropyl carbamate, n-butylammonium n -Butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t-butyl carbamate, 2-ethylhexyl ammonium 2-ethylhexyl carbamate, octadecylammonium octadecyl carbamate, 2-methoxyethylammonium 2 -Methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimine Ammonium hexamethyleneiminecarbamate, morpholinium morpholincarbamate, pyridinium ethylhexylcarbamate, triethylenediamine isopro Philbicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethylcarbonate, isopropylammonium isopropylcarbonate, isopropylammonium bicarbonate, n-butylammonium n-butyl Carbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium bicarbonate, 2-methoxyethylammonium 2-methoxyethylcarbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethylcarbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutyl Carbonate, dioctadecyl ammonium dioctadecyl carbonate, dioctadecyl ammonium bicarbonate, Tyldecyl ammonium methyldecyl carbonate, hexamethylene imine ammonium hexamethylene imine carbonate, morpholine ammonium morpholin carbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbonate, pyridinium bicarbonate, triethylene dia Aluminum isopropyl carbonate, triethylene dimethyl bicarbonate, and derivatives thereof.

In addition, the kind and manufacturing method of the said ammonium carbamate or ammonium carbonate type compound do not need to restrict in particular. For example, US Pat. No. 4,542,214 (September 17, 1985) describes ammonium carbamate-based compounds from carbon dioxide and primary amines, secondary amines, tertiary amines or at least one of these mixtures, and water per mole of amine. When 0.5 mol is used, an ammonium carbonate compound is obtained, and when it is 1 mol or more, an ammonium bicarbonate compound can be obtained. In this case, when prepared directly or without using a solvent under normal pressure or pressure, alcohols such as water, methanol, ethanol, isopropanol and butanol, glycols such as ethylene glycol and glycerin, ethyl acetate, butyl acetate, carbitol acetate and Acetates, diethyl ether, tetrahydrofuran, ethers such as dioxane, methyl ethyl ketone, ketones such as acetone, hydrocarbons such as hexane, heptane, aromatics such as benzene, toluene, and chloroform, methylene chloride, carbon Halogen-substituted solvents such as tetrachloride, or a mixed solvent thereof, and the like, and carbon dioxide may be bubbled in a gaseous state or use solid dry ice, and may react in a supercritical state. In addition to the above-described methods, any known method may be used to prepare the ammonium carbamate or ammonium carbonate derivative used in the present invention as long as the final material has the same structure. That is, it does not need to specifically limit the solvent, reaction temperature, a concentration, or a catalyst for manufacture, and can also manufacture yield.

An organic silver complex compound may be prepared by reacting the ammonium carbamate or ammonium carbonate compound and the silver compound thus prepared. For example, at least one silver compound as shown in formula (1) and at least one ammonium carbamate or ammonium carbonate derivative as shown in formula (2), formula (3) or formula (4) and mixtures thereof may be subjected to atmospheric pressure or When reacting directly or without using a solvent under pressure, alcohols such as water, methanol, ethanol, isopropanol, butanol, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate and carbitol acetate, Ethers such as diethyl ether, tetrahydrofuran, dioxane, ketones such as methyl ethyl ketone, acetone, hydrocarbons such as hexane and heptane, aromatics such as benzene and toluene, and chloroform, methylene chloride and carbon tetrachloride Halogen substituted solvents or their The sum may be a solvent or the like. In addition, in preparing the silver complex compound, a silver complex compound obtained by reacting carbon dioxide after preparing a solution in which the silver compound of Formula 1 is mixed with one or more amine compounds in addition to the above-described method can be used in the present invention. In this case, as in the above, the reaction may be performed without using a solvent at atmospheric pressure or under pressure, or by using a solvent. However, the organic silver complex compound production method of the present invention does not need to be particularly limited. That is, as long as the structure of the final material is the same, any known method may be used. For example, there is no need to specifically limit the solvent for the preparation, the reaction temperature, the concentration, the presence or absence of the use of a catalyst, and the like, and the production yield is also acceptable.

The composition of the transparent silver ink of the present invention is a primary amine, secondary amine, tertiary amine compound or the above ammonium carbamate, carbonate, bicarbonate-based compound or at least one of these mixtures as the silver complex compound and stabilizer. It consists of. That is, specifically as a stabilizer, for example, as an amine compound, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethyl Hexylamine, n-heptylamine, n-octylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine , Allylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanolamine, methoxyethylamine, 2-hydroxypropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n- Butoxyamine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, diethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, pipepe Razine, Ethylenediamine, Propylenediamine, Hexamethylenediamine, Tri Ethylenediamine, 2,2- (ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, aniline, anisidine, aminobenzonitrile, benzylamine and derivatives thereof, and polymer compounds such as polyallylamine or polyethyleneimine and derivatives thereof, and the like, and the like.

And as a stabilizer ammonium carbamate, carbonate, bicarbonate-based compound specifically for example ammonium carbamate (ammonium carbamate), ammonium carbonate (ammonium carbonate), ammonium bicarbonate, ethylammonium ethyl carbamate, Isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecyl Ammonium Octadecyl Carbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarba Mate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinka Mate, pyridinium ethylhexyl carbamate, triethylenediaminium isopropylbicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethylcarbonate, isopropylammonium isopropylcarbonate , Isopropylammonium bicarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, t-butylammonium bicarbonate, 2-ethylhexyl ammonium 2-ethylhexyl carbonate, 2-ethylhexyl ammonium bicarbonate, 2-methoxyethylammonium 2-methoxyethylcarbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethylcarbonate, 2-cyanoethylammonium bicarbonate Carbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, diocta Cyl ammonium dioctadecyl carbonate, dioctadecyl ammonium bicarbonate, methyl decyl ammonium methyl decyl carbonate, hexamethylene imine ammonium hexamethylene imine carbonate, morpholine ammonium morphocarbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropyl ammonium tri Ethoxysilyl propyl carbonate, pyridinium bicarbonate, triethylene dimethyl isopropyl carbonate, tri ethylene dimethyl bicarbonate, its derivatives, etc. are mentioned. The amount of such stabilizer used is not particularly limited as long as it meets the ink characteristics of the present invention. However, the content is preferably 0.1% to 90%, more preferably 1% to 50%, even more preferably 5% to 30% in molar ratio with respect to the silver compound. If it exceeds this range, the conductivity of the thin film may occur, and in the following, the storage stability of the ink may be deteriorated. The deterioration of the storage stability of the ink eventually leads to a failure of the coating film, and furthermore, the stabilizer is not only storage stability but also uniform when the stabilizer in the above range is not used when the coating film is fired after coating the silver ink composition. Problems may occur in which a dense thin film may not be formed or cracks may occur.

In addition, solvents may be required to control the viscosity of the ink or to form a thin film. At this time, solvents such as water, methanol, ethanol, isopropanol, butanol, ethylhexyl alcohol and terpineol, ethylene glycol and glycerin Such as glycols, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, ethyl carbitol acetate, methyl cellosolve, butyl cellosolve, diethyl ether, tetrahydrofuran, dioxane and Ethers such as methyl ethyl ketone, acetone, dimethylformamide, ketones such as 1-methyl-2-pyrrolidone, hexane, heptane, paraffin oil, hydrocarbons such as mineral spirits, aromatics such as benzene, toluene, and chloroform Or halogen-substituted solvents such as methylene chloride and carbon tetrachloride, dimethyl sulfoxide It may be used as the mixed solvents thereof.

Meanwhile, the transparent silver ink composition of the present invention may be a binder resin, a reducing agent, a surfactant, a wetting agent, or the like, in addition to the silver complex compound, the stabilizer and the solvent. , Additives such as thixotropic agents or leveling agents and the like can be used as members of the ink composition. For example, binder resins that can be generally used are acrylic resins such as polyacrylic acid or polyacrylic acid esters, cellulose resins such as ethyl cellulose, aliphatic or copolyester-based resins, vinyl such as polyvinyl butyral, polyvinylacetate Thermoplastic resins, polyurethane resins, polyether and urea resins, alkyd resins, silicone resins, fluorine resins, olefin resins such as polyethylene, thermoplastic resins such as petroleum and rosin resins, epoxy resins, unsaturated polyester resins, phenols Thermosetting resins such as resin-based resins, melamine-based resins, acrylic resins having various structures of ultraviolet or electron beam curing, and ethylene-propylene-based rubbers and styrene-butadiene-based rubbers may also be used. Surfactants include anionic surfactants such as sodium lauryl sulfate, nonionic phenoxy-polyethoxyethanol, and nonionic surfactants such as Dupont's FsN. Active agents, and cationic surfactants such as laurylbenzylammonium chloride and amphoteric surfactants such as lauryl betaine and coco betaine. Wetting agents or wetting dispersants include polyethylene glycols, compounds such as the Suftenol series from Air Products, Tego Wet Series from Deguessa, and BYK from BYK as the thixotropic agents or leveling agents. BYK series, Degussa glide series, EFKA EFKA 3000 series, Cognis DSX series and the like can be used. In addition, reducing agents may be used to facilitate calcination, for example, hydrazine, acetichydrazide, sodium or potassium borohydride, trisodium citrate, and methyldiethanolamine, dimethylamineborane and Amine compounds such as amine compounds, ferrous chloride, ferric lactate, aldehyde compounds such as hydrogen, hydrogen iodide, carbon monoxide, formaldehyde, acetaldehyde, glucose, ascorbic acid, salicylic acid, tannic acid, pyrogarol ( pyrogallol) and organic compounds such as hydroquinone. In addition, in the preparation of the transparent silver ink composition of the present invention, in addition to the above method, a silver compound of Formula 1 and at least one excess amine compound or an ammonium carbamate or ammonium carbonate-based compound and a mixed solution thereof are prepared and If necessary, a silver ink composition obtained by adding carbon dioxide or the like after adding the binder or the additive may be prepared and used. In this case, as in the above, the reaction may be performed without using a solvent at atmospheric pressure or under pressure, or by using a solvent.

The transparent silver ink composition prepared in the present invention has excellent stability and solubility, and thus can be easily applied to coating or various printing processes. For example, metal, glass, silicon wafer, ceramic, plastic film such as polyester or polyimide, rubber sheet, Coatings can be made on substrates such as fibers, wood, paper, etc. to produce thin films or print them directly. Such substrates may be used after washing and degreasing or may be used by pretreatment. Pretreatment methods include plasma, ion beam, corona, oxidation or reduction, heat, etching, ultraviolet (UV) irradiation, and primers using the binder or additives described above. primer) treatment and the like. Thin film manufacturing and printing methods include spin coating, roll coating, spray coating, dip coating, flow coating, doctor blade and dispensing depending on the properties of the ink, respectively. Dispensing, inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexography printing, lithography and the like can be selected and used.

The silver ink viscosity of the present invention does not need to be particularly limited. That is, it is good if there is no problem in the method of manufacturing and printing the thin film, and may vary depending on the method and type. In the above printing method, for example, ink viscosity is important when forming a thin film and a pattern by inkjet printing, but the viscosity range is 0.1 to 50 cps, preferably 1 to 20 cps, and more preferably 2 to 15 cps. If it is lower than this range, the thickness of the thin film after firing may not be sufficient, so that the conductivity may be lowered. If the thickness is higher than the range, ink may not be smoothly discharged.

The thin film or pattern thus obtained can be used to form a metal or metal oxide pattern through an aftertreatment process such as oxidation or reduction treatment, heat treatment, infrared rays, ultraviolet rays, electron beams, and laser treatments. . The post-treatment step may be heat treated under a normal inert atmosphere, but may be processed in air, nitrogen, carbon monoxide, or even a mixed gas of hydrogen and air or another inert gas, if necessary. Heat treatment is usually between 80 to 400 ℃, preferably 80 to 300 ℃, more preferably 120 to 250 ℃ heat treatment is good for the properties of the thin film. In addition, heat treatment of two or more steps at low and high temperatures within the above range is also good for the uniformity of the thin film. For example, it is good to process for 3 to 30 minutes at 80-150 degreeC, and to process for 5 to 30 minutes at 150-300 degreeC.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the Examples are only illustrative of the present invention, and the scope of the present invention is not limited to the Examples.

EXAMPLES

Example 1

In a 250 milliliter Schlenk flask with a stirrer, 32.5 grams (107.5 mmol) of 2-ethylhexyl ammonium 2-ethylhexylcarbamate, a viscous liquid, was dissolved in 100 milliliters of methanol, followed by 10.0 grams of silver oxide (43.1). Mmol) was added and reacted at room temperature. As the reaction proceeded, the complex initially formed in a black suspension, the color faded, and finally a colorless transparent solution was obtained. The solvent was removed in vacuo from this reaction solution to obtain 42.0 grams of a white silver complex compound. To 20.0 grams of this silver complex, 5.3 grams of 2-ethylhexylamine was added as a stabilizer, and 8.47 grams of methanol was added as a solvent to prepare a transparent silver ink composition having a viscosity of 5.7 cps. The uniformity and density of the thin film obtained after applying the prepared ink composition was calcined at the temperature shown in Table 1 below, and the conductivity (surface resistance value) and adhesive force results measured after the measurement were shown in Table 1.

Comparative Example 1

A transparent silver ink composition having a viscosity of 5.5 cps was prepared using 23.8 grams of the silver complex compound prepared in Example 1 without using 2-ethylhexylamine as a stabilizer and 13.8 grams of methanol solvent. The conductivity (surface resistance value) and adhesive force measured after firing the thin film obtained after coating the prepared ink composition under the same conditions as in Example 1 are shown in Table 1 in comparison with Example 1. As a result, the conductivity was lowered or the adhesive strength was inferior, and the thin film was not uniformly applied, the pulling phenomenon was shown, and the cracking occurred in the density.

Comparative Example 2

5.0 grams of silver hexanoate was used instead of the silver complex compound of Example 1, and 5.3 grams of 2-ethylhexylamine and 5.54 grams of methanol solvent were added as a stabilizer to prepare a transparent silver ink composition having a viscosity of 5.6 cps. . The conductivity (surface resistance value) and adhesive force measured after firing the thin film obtained after coating the prepared ink composition under the same conditions as in Example 1 are shown in Table 1 in comparison with Example 1. As a result, not only the adhesion was significantly inferior, but the conductivity was too low, and there was little applicability.

Example 2

In a 250 milliliter Schlenk flask with a stirrer, 8.2 grams (86 mmol) of ammonium carbonate dissolved in 100 milliliters of methanol was mixed with 15.0 grams (250 mmol) of isopropylamine, followed by 10.0 grams of silver oxide (43.1). Mmol) was added and reacted at room temperature. As the reaction proceeded, the complex initially formed in a black suspension, the color faded, and finally a colorless transparent solution was obtained. The solvent was removed in vacuo from this reaction solution to obtain 28.4 grams of white silver complex compound. To 20.0 grams of this silver complex, 5.3 grams of 2-ethylhexylamine as a stabilizer and 8.47 grams of methanol were added as a solvent to prepare a transparent silver ink composition having a viscosity of 3.8 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 3

A silver complex compound was prepared from 37.2 grams of 2-ethylhexylammonium 2-ethylhexylcarbonate in place of the 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1, and a transparent silver ink having a viscosity of 5.6 cps in the same manner as in Example 1. The composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

       Example 4

A silver complex compound was prepared from 48.6 grams of 2-ethylhexylammonium 2-ethylhexylbicarbonate in place of the 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1, and was prepared in the same manner as in Example 1. An ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 5

Instead of the 2-ethylhexyl ammonium 2-ethylhexyl carbamate of Example 1 to prepare a silver complex compound of 32.0 grams of n-butylammonium n-butylcarbonate and 12.0 grams of silver carbonate instead of silver oxide, the viscosity was 8.5 in the same manner as in Example 1. A cps of clear silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 6

A silver complex compound was prepared using 28.2 grams of cyclohexylammonium cyclohexylcarbamate in place of the 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1, and a transparent silver ink composition having a viscosity of 4.3 cps was prepared in the same manner as in Example 1. Prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 7

A silver complex compound was prepared using 31.2 grams of benzyl ammonium benzyl carbamate instead of 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1 to prepare a transparent silver ink composition having a viscosity of 5.3 cps in the same manner as in Example 1. . Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 8

A silver complex compound was prepared using 30.8 grams of 2-methoxyethylammonium 2-methoxyethylbicarbonate instead of 2-ethylhexylammonium 2-ethylhexylcarbamate of Example 1, and the viscosity was measured in the same manner as in Example 1 to 2.8 cps. To prepare a transparent silver ink composition. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 9

A silver complex compound was prepared using 18.8 grams of isopropylammonium isopropyl bicarbonate and 25.0 grams of octyl ammonium octyl bicarbonate instead of 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1, and the viscosity was measured in the same manner as in Example 1. A transparent silver ink composition with cps was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 10

Silver complex compound of 19.7 grams of 2-ethylhexyl ammonium 2-ethylhexyl carbamate and 12.7 grams of 2-methoxyethylammonium 2-methoxyethylcarbamate instead of 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1 To prepare a transparent silver ink composition having a viscosity of 22.6cps in the same manner as in Example 1. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 11

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 5, 1.2 grams of ammonium carbonate and 0.05 grams of Efka 3650 (Efca) were added as stabilizers, and 25.0 grams of methoxypropyl acetate was added as a solvent to obtain a viscosity of 3.6 cps. A clear silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 12

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 5, 1.2 grams of 2,2-ethylenedioxybisethylamine and 0.05 grams of Efka 3650 (Efca Co.) were added as a stabilizer, and methoxypropyl acetate 25.0 was used as a solvent. Gram was added to prepare a clear silver ink composition with a viscosity of 3.2 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 13

To 12.0 grams of the silver complex compound prepared in the same manner as in Example 8, 0.2 g of tripropylamine and 0.03 g of BWK 373 (BKK) were added as stabilizers and 20.0 grams of 1-methoxypropanol was added as a solvent. A 3.3 cps clear silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 14

To 12.0 grams of the silver complex compound prepared in the same manner as in Example 8, 0.2 g of diisopropylamine and 0.03 g of BWK 373 (BKK) were added as stabilizers and 20.0 grams of 1-methoxypropanol was added as a solvent. A transparent silver ink composition was prepared having a viscosity of 4.2 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 15

To 12.0 grams of the silver complex compound prepared in the same manner as in Example 3, 0.2 grams of 3-methoxypropylamine and 0.03 grams of Tegowet 505 (Degussa) were added as a stabilizer, and 20.0 grams of ethanol was added as a solvent to give a viscosity of 4.2 cps. A transparent silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 16

To 12.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.03 grams of Tego Wet 505 (Degussa) were added as a stabilizer, and 20.0 grams of ethanol was added as a solvent to obtain a viscosity of 4.4 cps. A clear silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 17

To 12.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.03 grams of Tego Wet 505 (Degussa) were added as a stabilizer, and 20.0 grams of 1-propanol was added as a solvent to obtain a viscosity of 4.6. A cps of clear silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 18

To 12.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.02 grams of Lilanite H. Extra (Cognis) were added as stabilizers, and 12.7 grams of methyl cellosolve was added as a solvent. The addition made a transparent ink composition having a viscosity of 4.1 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 19

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.03 grams of Efka 3835 (Ephca Co.) were added as stabilizers and 12.7 grams of ethyl acetate was added as a solvent to give a viscosity of 6.5 cps. A transparent silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 20

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.05 grams of Efka 3777 (Efca) were added as stabilizers, and 12.7 grams of toluene were added as a solvent to obtain a viscosity of 6.3 cps. A clear silver ink composition was prepared. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 21

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.03 grams of Glide 410 (Degussa) were used as stabilizers, and 1-propanol and ethyl carbitol acetate were weight ratios of 2: 1. It was added to 12.7 grams of the mixed solvent to prepare a transparent silver ink composition having a viscosity of 6.2 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 22

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.03 grams of DSX 1514 (Cognis) were used as stabilizers. N, N-dimethylformamide and N, N-dimethyl Sulfooxide and methanol were added to 12.7 grams of a solvent mixed at a weight ratio of 3: 1: 1 to prepare a transparent silver ink composition having a viscosity of 7.8 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 23

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.1 gram of Efka 410 (Efca Co., Ltd.) were used as stabilizers, and 1-methyl-2-pyrrolidone and 2-butanol A transparent silver ink composition having a viscosity of 6.7 cps was added to 12.7 grams of mixed solvent in a weight ratio of 4: 1. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 24

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 3, 3.4 grams of 2-ethylhexylamine and 0.05 grams of Surinol 465 (Air Products) as a stabilizer were added to water, polyethylene glycol (PEG) 200 and methanol 2: 12.7 grams of mixed solvents were added at a weight ratio of 1: 1 to prepare a transparent silver ink composition having a viscosity of 8.9 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 25

In a 250 milliliter Schlenk flask with a stirrer, 26 g (0.20 mole) of 2-ethylhexylamine, 15 g (0.20 mole) of n-butylamine and 10 g of methanol as a solvent were stirred, followed by 9.3 g of silver oxide. After adding (0.04 mol), carbon dioxide gas was allowed to react while slowly bubbling at room temperature. At this time, as the reaction proceeded, the complex first formed in a black suspension (Slurry), the color faded, and finally a colorless transparent solution was obtained. This solution was filtered through a 0.45 micron filter to obtain a clear transparent liquid silver complex compound. To 20.0 grams of this silver complex compound, 3.5 grams of 2-ethylhexylamine and 0.05 grams of Efka 3650 (Efca Co.) were added to prepare a transparent silver ink composition having a viscosity of 15.4 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 26

After adding 26 grams (0.20 mol) of 2-ethylhexylamine, 15.0 grams (0.20 mol) of n-butylamine and 0.24 grams of dodecylamine to a 250 milliliter pressurized vessel equipped with a stirrer, Leelanite H. Extra (Cognis) Add 0.03 grams and 10.0 grams methanol and stir. After adding 9.3 grams (0.04 mol) of silver oxide, the reaction was carried out while slowly injecting carbon dioxide gas at room temperature to obtain a clear transparent silver ink having a viscosity of 135.0 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 27

4.8 grams of ethyl cellulose was added to 20.0 grams of the silver complex compound prepared in the same manner as in Example 10 to prepare a transparent silver ink composition having a viscosity of 2,300 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 28

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 10, 2.0 grams of 2-ethylhexylammonium 2-ethylhexylcarbamate was added to prepare a transparent silver ink composition having a viscosity of 19.2 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 29

To 20.0 grams of the silver complex compound prepared in the same manner as in Example 10, 3.4 grams of 2-ethylhexylamine, 0.8 grams of polyvinyl butyral (BL-18 manufactured by Barker), and 4.0 grams of butyl cellosolve were added as stabilizers. A transparent silver ink composition was prepared having a viscosity of 8,000 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 30

A silver complex compound was prepared from 20.1 grams of isopropylammonium isopropyl carbonate instead of 2-ethylhexylammonium 2-ethylhexyl carbamate of Example 1, and 3.4 grams of 2-ethylhexylamine as a stabilizer was added to 20.0 grams of the silver complex compound. Instead of methanol, 12.7 grams of water and 0.03 grams of coco betaine were added as a solvent to prepare a transparent silver ink composition having a viscosity of 3.5 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 31

20.1 grams of isopropylammonium isopropyl carbonate and 13.0 grams of water were added to a 250 milliliter Schlenk flask equipped with a stirrer and stirred. Then, 10.0 grams (43.1 mmol) of silver oxide was added and reacted at room temperature to dissolve in water. A silver complex compound was prepared, and 3.4 g of 2-ethylhexylamine and 0.03 g of coco betaine were added to 43.1 g of the liquid silver complex compound to prepare a transparent silver ink composition having a viscosity of 3.5 cps. Table 1 shows the conductivity (surface resistance value) and adhesive force results measured after firing the uniform and dense thin film obtained after applying the prepared ink composition.

Example 32

A transparent silver ink having a viscosity of 3.8 cps prepared in Example 2 was filled in a polyethylene container and patterned on a PET film using a flatbed printer equipped with a piezo inkjet printer head F083000 (trade name: Epson). The patterned sample was heat-treated at 80 ° C. for 5 minutes and at 130 ° C. for 10 minutes.

Example 33

The transparent silver ink having a viscosity of 2,300 cps prepared in Example 26 was patterned on a PET film using a 320 mesh patterned silk screen printing machine. The patterned samples were heat treated at 100 ° C. for 3 minutes and at 130 ° C. for 10 minutes.

Example 34

The transparent silver ink having a viscosity of 19.2 cps prepared in Example 27 was patterned on a PET film pretreated with polyvinyl butyral resin using a gravure printing machine. The patterned samples were heat treated at 80 ° C. for 2 minutes, at 100 ° C. for 3 minutes, and at 130 ° C. for 5 minutes.

Table 1 Properties data of silver coating films prepared in Examples and Comparative Examples

(1) Adhesive force evaluation: The state where a silver film is transferred to an adhesive surface is evaluated by sticking Scotch tape (trade name: 3M company make) on a printing surface, and peeling.

(Circle): When there is no transfer of a silver thin film in the adhesive surface of a tape

(Triangle | delta): When a part of silver thin film is transferred to the adhesive surface of a tape, and it isolate | separates from a base material

      ×: most of the silver thin film is transferred to the adhesive side of the tape and separated from the base

(2) Conductivity evaluation: After making a rectangular sample of pattern 1cm × 3cm, measure the sheet resistance with AIT CMT-SR1000N.

According to the present invention, a silver complex compound obtained by reacting at least one silver compound represented by the formula (1) with at least one ammonium carbamate or ammonium carbonate compound represented by the formula (2), (3) or (4) and a primary amine as a stabilizer, A silver ink composition is provided comprising a secondary amine, tertiary amine compound or ammonium carbamate, carbonate, bicarbonate-based compound or at least one of these mixtures.

The ink composition has excellent stability and solubility, is easy to form a thin film, and is easily baked at a low temperature of 150 ° C. or lower to form a thin film or pattern having a high conductivity regardless of the type of substrate. It can be coated on a substrate such as plastic film, rubber sheet, fiber, wood, paper, such as polyester or polyimide, can be manufactured or printed directly. Thin film manufacturing and printing methods include spin coating, roll coating, spray coating, dip coating, flow coating, doctor blade and dispensing depending on the properties of the ink, respectively. Various methods such as dispensing, inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexography printing and lithography can be used.

In addition, when the composition of the present invention is used, the coating film is uniformly formed, and the conductivity and adhesion of the formed coating film are shown in a suitable range in the technical field. In addition to the above properties, cracking of the coating film does not occur, thereby significantly improving quality. The color of the other ink coating film also has the effect of expressing clearly.

In addition, the ink of the present invention can be used for the production of silver powder, paste, colloid or nanoparticles, electromagnetic shielding material, conductive adhesive, low resistance metallization, printed circuit board (PCB), flexible circuit board (FPC), wireless Antennas for RFID tags, solar cells, secondary or fuel cells, and plasma displays (PDPs), liquid crystal displays (TFT-LCDs), organic light-emitting diodes (OLEDs), flexible displays and organic thin film transistors OTFT) and the like to provide an excellent composition that can be used as an electrode or a wiring material.

Claims (30)

A silver ink composition containing 1 to 99% by weight of a silver complex compound obtained by reacting at least one silver compound of Formula 1 with at least one compound selected from Formulas 2 to 4. (Formula 1)

(N is an integer of 1 to 4, X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoro Substituents selected from borate, acetylacetonate, carboxylate and derivatives thereof) (Formula 2)

(Formula 3)

(Formula 4)

(The R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different from each other, hydrogen, an aliphatic or alicyclic alkyl group having 1 to 30 carbon atoms or an aryl group or an aralkyl group, a functional group Is a substituent selected from substituted alkyl and aryl groups, heterocyclic compound groups, polymer compound groups and derivatives thereof.) The method of claim 1, The silver ink composition is a silver ink composition, characterized in that it further comprises one or more amines selected from primary, secondary amines or tertiary amines, or any one or more compounds selected from Formulas 2 to 4 as a stabilizer. (Formula 2)

(Formula 3)

(Formula 4)

(The R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different from each other, hydrogen, an aliphatic or alicyclic alkyl group having 1 to 30 carbon atoms or an aryl group or an aralkyl group, a functional group Is a substituent selected from substituted alkyl and aryl groups, heterocyclic compound groups, polymer compound groups and derivatives thereof.) The method of claim 2, The silver ink composition is a transparent silver ink composition further comprises any one or more components selected from binder resins, reducing agents or additives. The method of claim 3, wherein The binder resin is any selected from acrylic, cellulose, polyester, polyether, vinyl, urethane, urea, alkyd, silicone, fluorine, olefin, petroleum, rosin, epoxy, unsaturated polyester, phenol, melamine-based resin and derivatives thereof. Transparent silver ink composition, characterized in that one or more. The method of claim 3, wherein The reducing agent is a transparent silver ink composition, characterized in that any one or more selected from a reducing amine compound, a metal salt or an organic compound. The method of claim 5, The reducing agent is hydrazine, acetichydrazide, sodium or potassium borohydride, trisodium citrate, methyldiethanolamine, dimethylamineborane, ferrous chloride, iron lactate, hydrogen, hydrogen iodide, carbon monoxide, formaldehyde, acetaldehyde Transparent silver ink composition, characterized in that any one or more selected from glucose, ascorbic acid, salicylic acid, tannic acid, pyrogarol, hydroquinone and derivatives thereof. The method of claim 3, wherein Transparent silver ink composition, characterized in that the additive is any one or more selected from surfactants, wetting agents, thixotropic agents or leveling agents. The method of claim 1, The silver ink composition is a silver ink composition, characterized in that it further comprises a solvent. The method of claim 8, The solvent is water, methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, ethylhexyl alcohol, terpineol, ethylene glycol, glycerin, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, ethyl carbitol Acetate, methyl cellosolve, butyl cellosolve, diethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, dimethylformamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, hexane, heptane Transparent paraffin oil, mineral spirits, toluene, xylene, chloroform, acetonitrile any one or more selected from the transparent silver ink composition The method of claim 1, The silver compound is silver oxide, thiocyanated silver, silver cyanide, silver cyanated silver, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoroborate, silver acetylacetonated silver And silver acetate, lactic acid silver, oxalic acid silver and derivatives thereof. The method of claim 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ independently of one another are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl , Nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, methoxyethyl, methoxypropyl, cyanoethyl, ethoxy, butoxy Methoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, pyrrole, Those selected from imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl, polyallylamine, polyethyleneamine and derivatives thereof A transparent silver ink composition, characterized in that. The method of claim 1, The compounds of Formulas 2 to 4 are ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ammonium bicarbonate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butylammonium n -Butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t-butyl carbamate, 2-ethylhexyl ammonium 2-ethylhexyl carbamate, octadecylammonium octadecyl carbamate, 2-methoxyethylammonium 2 -Methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimine Ammonium hexamethyleneiminecarbamate, morpholinium morpholincarbamate, pyridinium ethylhexylcarbamate, triethylenediaminium isopropyl Bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethylcarbonate, isopropylammonium isopropylcarbonate, isopropylammonium bicarbonate, n-butylammonium n-butylcarbonate , Isobutylammonium isobutyl carbonate, t-butylammonium t-butylcarbonate, t-butylammonium bicarbonate, 2-ethylhexyl ammonium 2-ethylhexyl carbonate, 2-ethylhexyl ammonium bicarbonate, 2-methoxyethylammonium 2 -Methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethylcarbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecyl carbonate, dibutylammonium dibutyl carbonate , Dioctadecyl ammonium dioctadecyl carbonate, dioctadecyl ammonium bicarbonate, Decylammonium methyldecylcarbonate, hexamethyleneimineammonium hexamethyleneimine carbonate, morpholine ammonium morphocarbonate, benzyl ammonium benzylcarbonate, triethoxysilylpropylammonium triethoxysilylpropylcarbonate, pyridinium bicarbonate, triethylenediamine Transparent silver ink composition, characterized in that any one or more selected from propyl carbonate, triethylene dimethyl bicarbonate and derivatives thereof. delete The method of claim 2, The amine compound is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octyl Amine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, allylamine, hydroxyamine, ammonium hydroxide Said, methoxyamine, 2-ethanolamine, methoxyethylamine, 2-hydroxy propylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxyamine, 2-hexyloxyamine, methoxy Methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, diethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine , Triethylenediamine, 2,2- (ethylenedioxy) bisethyl Amine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aniline, anisidine, aminobenzonitrile, benzyl Transparent silver ink composition, characterized in that any one or more selected from amine, polyallylamine, polyethyleneimine and derivatives thereof. The method of claim 2, Transparent silver ink composition, characterized in that the content of the stabilizer is selected in the range of 0.1% to 90% by molar ratio with respect to the silver compound. The method of claim 1, Transparent silver ink composition, characterized in that X is oxygen, carbonate, nitrate or nitrite or silver compound. An amine compound selected from one or more silver compounds of Formula 1 and primary amines, secondary amines, tertiary amines or mixtures thereof is added at a rate of 2 to 50 mole times with respect to the silver compounds, followed by bubbling carbon dioxide Transparent silver ink composition, characterized in that for producing a. (Formula 1)

(N is an integer of 1 to 4, X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoro Substituents selected from borate, acetylacetonate, carboxylate and derivatives thereof) The method of claim 17, The silver ink composition is a transparent silver ink composition, characterized in that further using any one or more components selected from binder resins, solvents, reducing agents and additives. The silver ink composition of any one of claims 1 to 12 and 14 to 18 is coated to form a thin film, and then subjected to oxidation treatment, reduction treatment, heat treatment, infrared ray, ultraviolet ray, electron beam or laser treatment. To form a thin film. The method of claim 19, The thin film is a method for forming a thin film, characterized in that formed by applying on the substrate. The method of claim 20, Wherein said substrate is selected from metals, glass, silicon wafers, ceramics, polyesters, polyimides, rubber sheets, fibers, wood, paper, and the like. The method of claim 20 or 21, A method of forming a thin film, characterized in that the substrate is pre-treated and used. The method of claim 22, A method for forming a thin film, characterized in that the pretreatment method is selected from plasma, ion beam, corona, oxidation or reduction, heat, etching, ultraviolet (UV) irradiation, primer treatment and the like. The method of claim 19, And the heat treatment is performed under air, nitrogen, argon, carbon monoxide, hydrogen, or a mixed gas thereof. The method of claim 19 A method of forming a thin film, characterized in that the heat treatment is carried out in the temperature range of 80 to 300 ℃. The method of claim 19, The heat treatment is a method of forming a thin film comprising the step of treating for 3 to 30 minutes at 80 to 150 ℃, and for 5 to 30 minutes at 150 to 300 ℃. The method of claim 19, And said coating is selected and applied by spin coating, roll coating, spray coating, dip coating, flow coating, or a doctor blade method. The method of claim 19, Wherein said coating is performed by a printing method selected from dispensing, inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexo printing or litho printing. The method of claim 19, The coating is a method of forming a thin film, characterized in that the silver composition is dissolved in water, alcohol, glycol, acetate, ether, ketone, aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon solvent. The method of claim 29, The solvent is water, methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, ethylhexyl alcohol, terpineol, ethylene glycol, glycerin, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, ethyl carbitol Acetate, methyl cellosolve, butyl cellosolve, diethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, dimethylformamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, hexane, heptane Paraffin oil, mineral spirits, toluene, xylene, chloroform, acetonitrile any one or more selected from a method for forming a thin film.

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