WO2009116782A2

WO2009116782A2 - Multi-functional coating solution composition

Info

Publication number: WO2009116782A2
Application number: PCT/KR2009/001333
Authority: WO
Inventors: 정광춘; 조현남; 유지훈; 김동립
Original assignee: 주식회사 잉크테크
Priority date: 2008-03-18
Filing date: 2009-03-17
Publication date: 2009-09-24
Also published as: CN103665995A; KR101675493B1; CN103665995B; WO2009116782A3; CN101978006B; KR20090099646A; CN101978006A

Abstract

The present invention relates to a multi-functional coating solution composition containing a silver compound as a main ingredient, and more particularly, to a multi-functional coating solution composition containing silver complexes of specific structures and a metal or nonmetal compound or at least one or more mixtures thereof. The multi-functional coating solution composition of the present invention is capable of being a wide variety of colors as well as a simple silver color, and exhibiting effects of multiple functions, i.e. at least one of the following: electricity and/or heat conductivity, antibacterial properties, anti-static electricity properties, anion and far infrared ray radiation properties, and reflective properties.

Description

Composite function coating liquid composition

The present invention relates to a composite functional coating liquid composition containing a silver compound as a main component, and more particularly, to a composite functional coating liquid composition containing a silver complex compound having a special structure and a metal or nonmetallic compound or at least one or more of these mixtures. .

Silver (Ag) has been used in various fields such as decoration, coin, tableware, electricity, electrical appliances, lighting, copiers, display electrodes, electromagnetic shielding, antibacterial as a precious metal because of its special characteristics including excellent electrical conductivity and antibacterial activity. For the product, it is preferred to have a multi-functional coating that can realize various colors other than the characteristics of silver, such as conductivity, antibacterial, gloss, antistatic, anion and far infrared radiation.

Commonly known coating methods include plating, magnetron sputtering, ion plasma deposition, chemical vapor deposition, physical vapor deposition, dip coating, fluidized bed coating, atomic layer deposition (ALD) coating. Method, spray coating method, spin coating method, electrodeposition coating method, electrostatic coating method, gravure coating method and the like are used and these methods can be applied to silver coating, of course. As a silver coating liquid composition used by reducing only a general silver precursor, in order to simultaneously provide various properties other than the basic properties of silver, a primer coating or another functional coating on the silver coating may be added to the substrate in addition to the silver coating method. Only then can it be given multifunctional characteristics. In addition, due to the multifunctionality, the performance of silver properties such as electrical conductivity, antimicrobial activity, antistatic, negative ion and far infrared radiation, glossiness is deteriorated. Recently, the related research is actively progressed, but there is a problem that the process for complex function grant is complicated and not easy.

As described above, the silver coating composition according to the prior art has various disadvantages such as high manufacturing cost or low functionality of the coating itself, which requires a complicated manufacturing process in order to give a coating effect of a complex function. Accordingly, the present invention provides a coating liquid composition and a method of preparing the same, which can realize various colors while simplifying the manufacturing process and exhibit complex functional effects such as electrical and / or thermal conductivity, antimicrobial properties, antistatic properties, anion and far infrared radiation or reflection characteristics. The purpose is to provide.

In addition, the present invention has another object to provide a method for producing a composite functional coating film to form a composite functional coating film on a variety of substrates using the composite functional coating liquid composition.

The inventors of the present invention have repeatedly studied to achieve the above-mentioned problems, and according to the type and content of the metal or nonmetallic compound added to the silver complex compound coating liquid having a special structure, in addition to the color development, electrical and / or thermal conductivity, antimicrobial or reflective properties The present invention has been accomplished by the discovery that different functionality may be implemented.

The present invention relates to a composite functional coating liquid composition containing a silver complex compound as a main component, and more particularly, to a silver complex compound having a special structure and a silver compound comprising a metal compound or a nonmetallic compound or at least one of these mixtures. It relates to a composite function coating liquid composition and a method for preparing the same. The combined function means that in addition to the color development function, it further has a function selected from electrical and / or thermal conductivity, antimicrobial, antistatic, anion and far infrared radiation or reflection properties.

In addition, the present invention is a composite functional coating of the composite functional coating film to form a coating film having a variety of color development and other functionalities on the surface of the various substrates, that is, selected from electrical and / or thermal conductivity, antimicrobial or reflective properties using the composite functional coating liquid It provides a manufacturing method.

When the multifunctional coating solution according to the present invention is used, alumina, titanium oxide-coated mica or glass flakes can be used as pearl pigments having various colors other than silver, and coated on ABS or PC to master After the chip is manufactured, compounding according to the ratio and using a process such as injection or extrusion can produce a plastic product having various antibacterial properties. In addition, when coated on aluminum or copper fine powder, it is possible to make a conductive material excellent in electrical conductivity, oxidation stability and economical efficiency.

In order to achieve the above object, the present invention provides a composite functional coating liquid composition for producing a composite functional coating film having a variety of color development and other functionalities, that is, a functional selected from electrical and / or thermal conductivity, antimicrobial or reflective properties. The composite function coating liquid composition includes a silver complex compound; And a color expressing agent selected from metal compounds, nonmetal compounds or mixtures thereof.

In addition, the method for producing a composite functional coating film having excellent surface properties according to the present invention includes the following manufacturing steps.

(i) preparing a silver coating liquid containing a silver complex compound;

(ii) preparing a complex functional coating solution by adding a color expression agent to the silver coating solution; And

(iii) applying the composite functional coating solution to a substrate to form a composite functional coating film.

The silver complex compound according to the present invention may be a silver compound, an ammonium carbamate-based compound, an ammonium carbonate-based compound, or an ammonium bicarbonate-based compound such as a silver complex compound known from Korean Patent Application No. 2006-0011083 filed by the present applicant. The silver complex compound of Ag [ammonium carbamate type compound, ammonium carbonate type compound, or ammonium bicarbonate type compound] composite structure manufactured by reaction with 1 type, or 2 or more types of mixtures chosen from a compound is meant.

Hereinafter, the present invention will be described in detail.

The present invention provides a silver complex compound prepared by reacting a silver compound represented by Formula 1 with an ammonium carbamate compound of Formula 2, an ammonium carbonate compound of Formula 3, an ammonium bicarbonate compound of Formula 4, or a mixture thereof; And

It provides a composite functional coating liquid composition containing a color expression agent selected from metal compounds, non-metal compounds or mixtures thereof.

In addition, the present invention is prepared by reacting (i) a silver compound represented by the following formula (1), an ammonium carbamate compound of formula (2), an ammonium carbonate compound of formula (3), an ammonium bicarbonate compound of formula (4) or a mixture thereof Preparing a silver coating liquid containing the silver complex compound;

(iii) applying the composite functional coating solution to a substrate to form a composite functional coating film;

It provides a method for producing a composite function coating film having excellent surface properties, including.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[In the above formula,

X is from oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, carboxylate and derivatives thereof Is a substituent selected,

n is an integer of 1~4, R ₁ to R ₆ are independently hydrogen, hydroxy, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkyl, C ₃ -C ₃₀ in the cycloalkyl, C ₆ to each other -C ₂₀ aryl, (C ₆ -C ₂₀ ) ar (C ₁ -C ₃₀ ) alkyl, functional substituted C ₁ -C ₃₀ alkyl, C ₆ -C ₂₀ aryl, heterocyclic compound, high molecular compound or Derivative thereof, and R ₁ to R ₆ may include a hetero element selected from N, S and O in the carbon chain when the functional group is a substituted or unsubstituted alkyl group or aralkyl group, and R ₁ and R ₂ or R ₄ And R ₅ may be independently connected to each other to C ₁ -C ₁₀ alkylene with or without a hetero atom to form a ring.]

Specific examples of the silver compound of Formula 1 include silver oxide, thiocyanated silver, silver sulfide, silver chloride, silver cyanide, silver cyanated silver, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate And silver perchlorate, silver tetrafluoride silver, acetylacetonated silver, silver acetate, silver lactate, silver oxalate and derivatives thereof, and the like.

R ₁ to R ₆ of Formulas 2 to 4 are specifically, for example, 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, hydroxyethyl, methoxyethyl, 2-hydroxypropyl, methoxypropyl, Cyanoethyl, ethoxy, butoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylene Diamine, triethylenediamine, pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and derivatives thereof, and poly With allylamine or polyethyleneimine There is no particular limitation thereto may be selected from polymeric compounds and derivatives thereof.

Specifically, for example, the ammonium carbamate-based compound of Formula 2 is ammonium carbamate, 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-methoxyethylcarba Mate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarba Mate, morpholinium morpholine carbamate, pyridinium ethylhexyl carbamate, triethylenedium isopropyl bicarbamate, benzyl ammo And one or two or more mixtures selected from the group consisting of nium benzyl carbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, and derivatives thereof, and the ammonium carbonate compound of Formula 3 may be ammonium carbonate ammonium carbonate, ethylammonium ethylcarbonate, isopropylammonium isopropylcarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, 2-ethylhexylammonium 2-ethyl Hexylcarbonate, 2-methoxyethylammonium 2-methoxyethylcarbonate, 2-cyanoethylammonium 2-cyanoethylcarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, dioctadecylammonium dioctadecyl Carbonate, methyldecylammonium methyldecylcarbonate, hexamethyleneimineammonium hexa 1 or 2 or more types selected from thiyleneimine carbonate, morpholine ammonium morphocarbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropylammonium triethoxysilylpropyl carbonate, triethylene dimethyl isopropyl carbonate, and derivatives thereof Examples of the ammonium bicarbonate compound of Formula 4 may include, for example, ammonium bicarbonate, isopropyl ammonium bicarbonate, t-butylammonium bicarbonate, 2-ethylhexyl ammonium bicarbonate, One or two or more mixtures selected from 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium bicarbonate, dioctadecylammonium bicarbonate, pyridinium bicarbonate, triethylenediadium bicarbonate and derivatives thereof Included.

The silver complex compound according to the present invention is described in the patent application No. 10-2006-0011083 filed by the present inventors, the preparation method, the silver complex compound can be separated into a solid from a solution state, the separated The solid is a complex consisting of silver ions (Ag ⁺ ) and anions (X ^n- ) and carbamate- or carbonate-based compounds of formulas (2) to (4), or the silver ions of the complex are partially reduced to aggregates of the following experimental structure. It is recognized that it has been converted.

[Equation]

Ag [A] _m

[A is a compound of Formula 2 to Formula 4, m is 0.7 to 2.5.]

In step (i), the silver coating liquid containing the silver complex compound may include a solvent in addition to the silver complex compound. Examples of the solvent include water, alcohols such as methanol, ethanol, isopropanol, butanol, glycols such as ethylene glycol and glycerin, ethyl acetate, butyl acetate, acetates such as carbitol acetate, diethyl ether, tetrahydrofuran and dioxane Ethers such as, methyl ethyl ketone, ketones such as acetone, hydrocarbons such as hexane, heptane, aromatics such as benzene and toluene, and halogen-substituted solvents such as chloroform, methylene chloride, carbon tetrachloride, or a mixed solvent thereof. Can be used.

Step (ii) is a step of preparing a composite functional coating solution composition by adding a color expression agent selected from a metal compound, a non-metal compound or a mixture thereof to a silver coating solution containing a silver complex compound.

For example, the metal compound to be added to the silver coating solution according to the present invention is described as Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu , Zn, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Tl, Ge, Sn, Pb Metal precursors such as Sb, Bi, As, Se, Eu, Sm, Th, Ac, Ce, Pr, or salts or oxides of the above organic acid metals, or alloy oxides, for example manganese oxalate, gold acetate, palladium oxalate, 2-ethyl hexanoate, cobalt octanoic acid, zirconium octanoic acid, cobalt stearate, nickel naphthalate, cobalt naphthalate, copper 2-ethyl hexanoate, iron stearate, nickel formate, calcium naphthenate, zinc Citrate, barium cerium neocatenate, copper cyanide, cobalt carbonate, platinum chloride, gold chloride, tetrabutoxy titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, acetoalkoxy al Minyum diisopropyl rate, a tin tetra flow borate, vanadium oxide, indium-there is tin oxide, tantalum methoxide, bismuth acetate, dodecyl meokep rabbit gold, indium acetyl acetonate or the like can be selected is not particularly limited thereto.

In addition, the metal compound may be in the form of a sphere, a linear, a plate, or a mixture thereof, and may be in a particle state including nanoparticles, or as a powder, flake, colloid, or hybrid. (hybrid), paste (sol), sol (sol), solution (solution) state or may be used in a variety of states, such as a mixture of one or more selected.

The nonmetallic compound added to the silver coating solution is 3-aminopropyltriethoxysilane, methyltriethoxysilane, tetraethylorthosilicate, vinyltriethoxysilane, vinylmethyldimethoxysilane, octyltriethoxysilane, phenylgamma Silicone compounds selected from aminopropyltrimethoxysilane, aminonehexyltrimethoxysilane and the like; 2-2-bis-4-hydroxyphenylhexafluoropropane, 3,5-bistrifluoromethylaniline, dotecafluoro-1-heptanol, 2-4-difluoroaniline, 4-fluoro Fluorine compounds selected from phenyl ester, dicaprobenzophenone, 2-fluorobiphenyl, tetrafluorohydroquinone and the like; Polypropylene, Polycarbonate, Polyacrylate, Polymethylmethacrylate, Cellulose Acetate, Polyvinylchloride, Polyurethane, Polyester, Alkyd Resin, Epoxy Resin, Melamine Resin, Phenolic Resin, Phenol Modified Alkyd Resin, Epoxy Modified Alkyd Resin Organic polymer resins selected from vinyl modified alkyd resins, silicone modified alkyd resins, acrylic melamine resins, polyisocyanate resins, epoxy ester resins, and the like may be used, but are not limited thereto.

The content of the color expression agent added to the silver coating solution is not particularly limited as long as it corresponds to the coating solution composition properties of the present invention. Usually the amount used is preferably in the range of 0.01 to 30 percent, more preferably 0.1 to 10 percent by weight, based on the total composition. When the content of the color expression agent is less than 0.01% by weight, the effect of expressing color is insignificant, and when the content is more than 30% by weight, the content of the silver complex compound or other components is relatively low so that the content of the coating film is different. This is because the characteristics may be degraded.

The complex functional coating liquid composition prepared in step (ii) may be a solvent, a stabilizer, a dispersant, a binder resin, a reducing agent, a surfactant, a humectant, as necessary, in addition to the silver complex compound and the color expression agent. additives such as wetting agents, thixotropic agents or leveling agents may be included.

The solvent contained in the coating solution may be selected from water, alcohols, glycols, acetates, ethers, ketones, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbon-based solvents, specifically, water, methanol, ethanol, isopropanol, 1-meth Oxypropanol, 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, dodecane, paraffin oil, mineral spirits, benzene, toluene, At least one selected from xylene, chloroform, methylene chloride, carbon tetrachloride and acetonitrile can be used. Can be.

Stabilizers contained in the coating solution may include a primary, secondary or tertiary amine compound with or without a hydroxy group; Ammonium salt compounds selected from ammonium carbamate-based, ammonium carbonate-based or ammonium bicarbonate-based compounds; Phosphorus compounds selected from phosphine, phosphite or phosphate compounds; Sulfur compounds selected from thiol or sulfide compounds; Or mixtures thereof. Specifically, for example, the amine compound is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n- Heptylamine, n-octylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, allylamine, hydroxide Hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanolamine, methoxyethylamine, 2-hydroxy propylamine, 2-hydroxy-2-methylpropylamine, methoxypropylamine, cyanoethylamine, Ethoxyamine, n-butoxyamine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, diethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine , Piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylene Amine, triethylenediamine, 2,2- (ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3- And amine compounds such as aminopropyltriethoxysilane, aniline, anidine, aminobenzonitrile, benzylamine and derivatives thereof, and polymer compounds such as polyallylamine and polyethyleneimine and derivatives thereof.

Step (iii) is a step of forming a composite functional coating film by applying the composite functional coating liquid prepared in step (ii) to the substrate.

The substrate used in the present invention may be any coating. For example, polyimide (PI), polyethylene terephthalate (PET), polyethernaphthalate (PEN), polyether sulfone (PES), nylon (Nylon), polytetrafluoroethylene (PTFE), polyether ether ketone ( Plastics such as PEEK), polycarbonate (PC), polyarylate (PAR) and the like; Resins such as various acrylic, urethane, fluorine, silicone epoxy, vinyl resins, and the like; Polymer rubber materials such as butyl rubber, chloroprene rubber, SBR, EPR, SIS rubber and the like; Various ceramic materials such as silica, alumina, titanium oxide, clay, stone, talc, mica and the like; Various metals or alloy materials such as aluminum, copper, nickel, iron, zinc and brass; Nonmetal materials such as carbon, carbon nanotubes (CNT), silicon, sulfur, and the like; Metal salt compounds such as salt, barium sulfate and the like; Various papers such as synthetic paper, photo paper, wrapping paper, corrugated paper, and the like; And various composite materials (composite) etc. which composited these materials can be used, and there is no need to restrict in particular.

In addition, the shape or shape of the substrate may be powder, flake, bead, ball, fiber, film, sheet, chip, rod ( rods, wires, whiskers, and the like may be used, but are not particularly limited thereto.

The composite functional coating liquid composition according to the present invention has a characteristic of imparting uniform coating properties to various substrates, and thus, excellent color expression due to the mixing of the silver complex compound and the color expression agent on the surfaces of various shapes and various materials as described above. In addition, there is an advantage to form a composite functional coating film exhibiting electrical and / or thermal conductivity, antimicrobial, antistatic, anion and far-infrared radiation or reflecting properties according to the silver component and color expression agent.

The coating method of the multi-functional coating solution is spin coating, roll coating, spray coating, dip coating, flow coating, and doctor blade, respectively, depending on the physical properties of the ink and the form of the substrate. ) And dispensing, inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexography printing, stencil printing, imprinting, xography, lithography lithography, fluidized bed coating, atomic layer deposition atomic layer deposition (ALD) coating, chemical vapor deposition (CVD), physical vapor deposition (PVD) ion plasma coating, electrostatic coating, electrodeposition coating One or more methods can be selected and used.

After the application of step (iii), drying, firing, or further drying and firing may be performed to form a coating film. When the type of substrate is plastic, resin, or rubber, it is preferable to form a coating film through a drying step after coating. The type of substrate is various ceramic materials, metal materials, carbon, carbon nanotubes (CNT), silicon, sulfur In the case of nonmetallic materials, metal salt compounds, and various kinds of papers, it is preferable to form a coating film by carrying out firing or by drying and firing. The drying and firing may be performed in an appropriate temperature range according to the type of substrate, but drying is preferably performed in a temperature range of 80 to 200 ° C. and firing of 300 to 700 ° C. This is because when the drying temperature is less than 80 ° C., the drying rate is not effective, and when the drying temperature is too high, the substrate may be denatured depending on the type of the substrate. This may be detrimental to the adhesion and the formation of a uniform coating film, and if it is too high above 700 ° C., may cause degeneration of the substrate and may be disadvantageous in terms of cost due to temperature rise.

The composite functional coating liquid composition according to the present invention may not only realize silver colors but also various colors, and sometimes have excellent effects such as electrical and / or thermal conductivity, antimicrobial properties, antistatic properties, anion and far infrared radiation or reflection characteristics, and the like. .

In addition, depending on the type and content of the metal or non-metallic compound added to the multi-functional coating liquid composition can be implemented different colors and functionality and can solve the existing complex processability.

The present invention will be described in more detail with reference to the following Examples. However, the following examples are merely examples of the present invention, and the claims of the present invention are not limited thereto.

Example 1

In a reactor equipped with a stirrer, 2.1 kilograms (6.94 mol) of 2-ethylhexyl ammonium 2-ethylhexyl carbamate and 0.825 kilograms (5.08 mol) of isobutylammonium isobutyl carbamate are dissolved in 5.2 kilograms of isopropanol, followed by 1 kilogram of silver oxide. (4.31 mol) was added and reacted at room temperature. The reaction solution was observed to initially turn black in color (Slurry), the reaction proceeds as the complex is produced, the color fades to become transparent and was reacted for 2 hours to give a colorless transparent solution. 0.125 kilograms of 2-hydroxy-2-methylpropylamine as a stabilizer was added to the solution, stirred, and filtered using a 0.45 micron membrane filter. The thermal analysis (TGA) showed a silver content of 10.05 wt%. Silver coating solution was prepared.

Example 2

Zirconium octoate (manufacturer: Jinyang Chemical) was added to 100 grams of the silver coating solution prepared in Preparation Example 1 to react at room temperature for 12 hours to prepare a stable composite functional coating solution solution.

Example 3

A composite functional coating solution was prepared in the same manner as in Example 1, except that calcium naphthenate (manufacturer: Jinyang Chemical) was added to 20 wt% to the silver coating solution prepared in Preparation Example 1.

Example 4

A multifunctional coating solution was prepared in the same manner as in Example 1, except that 3-aminopropyltriethoxysilane (manufacturer: Aldrich) was added to the solution prepared in Example 1 to 30 weight percent.

Example 5

A multifunctional coating solution was prepared in the same manner as in Example 1, except that polyurethane resin HW-1217 (manufacturer: Hosung Chemex) was added to 10 wt% in the solution prepared in Preparation Example 1.

Example 6

A composite functional coating solution was prepared in the same manner as in Example 1, except that titanium butoxide (manufacturer: Aldrich) was added to 5 wt% of the solution prepared in Preparation Example 1.

Example 7

Acetoalkoxy aluminum diisopropylate (Ajinomoto fine-techno, AL-M) was added to the solution prepared in Preparation Example 1 to 5 weight percent to prepare a composite functional coating solution.

Composite function coating film manufacturing

Using the above-described composite functional coating solution of Examples 1 to 7 as described in the Examples below, various composite functional coating films were prepared and the coating film characteristics were confirmed.

Example 8

After preparing a spin coating glass substrate for manufacturing a composite coating film, the surface of the glass substrate was first removed using ethanol, and then dried at 50 ° C. in a dryer. The glass substrate dried for 30 minutes or more was placed in a spin coater, and 20 ml of the composition of Example 2 was poured onto the glass substrate, rotated at 500 rpm to form a coating film, and then treated at 500 ° C. for 5 minutes. The color of the prepared coating film was shiny black, and a coating film having a sheet resistance of 12.4 μs / □ and a reflectance of 40% was formed.

Example 9

The coating solution prepared in Example 3 was formed on the surface of the glass substrate from which dust was removed using a spray coating machine, and then treated at 500 ° C. for 5 minutes. The color of the prepared coating film was shiny yellow, and a coating film having a sheet resistance of 150Ω / □ and a reflectance of 40% was formed.

Example 10

The coating solution prepared in Example 4 was formed on the surface of the PET film using a microgravure coating machine and then dried at 150 ° C. for 5 minutes. The color of the prepared coating film was formed a coating film showing a light red color.

Example 11

After putting 1Kg of glass flakes (manufacturer: NGF, product name: RCF-150) into a fluidized bed reactor and raising the internal temperature to 110 ° C., the coating liquid composition prepared in Example 5 was coated for 20 minutes while flowing and dried at 150 ° C. A gray pearl pigment was formed, which was put in a kiln again and fired at 500 ° C for 10 minutes to obtain a bright and shiny gray pearl pigment having a sheet resistance of 300 Ω / □ and a reflectance of 50%.

Example 12

1 kg of aluminum powder ECKA 20T (manufacturer: eckagranules) was placed in a fluidized bed reactor, and the internal temperature was raised to 110 ° C., and then the coating liquid composition prepared in Example 1 was coated for 20 minutes while flowing and then dried at 150 ° C., and the sheet resistance was 200 mΩ / □, silver electroconductive particle of 85% of reflectance was formed.

Example 13

The coating solution prepared in Example 6 was formed on the surface of the glass substrate using a dip coating machine and then treated at 500 ° C. for 5 minutes. The color of the prepared coating film was shiny black, and a coating film having a sheet resistance of 100 Ω / □ and a reflectance of 35% was formed.

Example 14

The coating solution prepared in Example 7 was formed on the surface of the PET film using a microgravure coating machine, and then dried at 150 ° C. for 5 minutes. The color of the prepared coating film was dark blue, a coating film showing a sheet resistance of 2K Ω / □ was formed.

The composite functional coating liquid composition according to the present invention may not only realize silver colors but also various colors, and sometimes has excellent electrical and / or thermal conductivity, antimicrobial properties, antistatic properties, anion and far infrared radiation or reflection characteristics, and the like.

Claims

(i) a silver complex compound prepared by reacting a silver compound represented by Formula 1 with an ammonium carbamate compound of Formula 2, an ammonium carbonate compound of Formula 3, an ammonium bicarbonate compound of Formula 4, or a mixture thereof; Preparing a silver coating liquid containing;

(ii) preparing a complex functional coating solution by adding a color expression agent to the silver coating solution; And

(iii) applying the composite functional coating solution to a substrate to form a composite functional coating film;

Method for producing a composite function coating film having excellent surface properties comprising a.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[In the above formula,

X is from oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, carboxylate and derivatives thereof Is a substituent selected,

n is an integer of 1~4, R 1 to R 6 are independently hydrogen, hydroxy, C 1 -C 30 alkoxy, C 1 -C 30 alkyl, C 3 -C 30 in the cycloalkyl, C 6 to each other -C 20 aryl, (C 6 -C 20 ) ar (C 1 -C 30 ) alkyl, functional substituted C 1 -C 30 alkyl, C 6 -C 20 aryl, heterocyclic compound, high molecular compound or Derivative thereof, and R 1 to R 6 may include a hetero element selected from N, S and O in the carbon chain when the functional group is a substituted or unsubstituted alkyl group or aralkyl group, and R 1 and R 2 or R 4 And R 5 may be independently connected to each other to C 1 -C 10 alkylene with or without a hetero atom to form a ring.]
The method of claim 1,

The color expression agent is selected from a metal compound, a non-metal compound or a mixture thereof and a method for producing a composite functional coating film containing 0.01 to 30% by weight based on the total weight of the composite functional coating solution.
The method of claim 2,

The metal compound is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, As, Se, Eu, Sm, A method for producing a composite functional coating film selected from a metal precursor, a metal organic acid salt, or a metal oxide comprising at least one metal selected from Th, Ac, Ce, and Pr.
The method of claim 3, wherein

The metal compound is manganese oxalate, gold acetate, palladium oxalate, copper 2-ethyl hexanoate, cobalt octanoic acid, zirconium octanoic acid, cobalt stearate, nickel naphthalic acid, cobalt naphthalic acid, copper 2-ethyl hexanoate Iron stearate, nickel formate, calcium naphthenate, zinc citrate, barium cerium neocatenate, copper cyanide, cobalt carbonate, platinum chloride, gold chloride, tetrabutoxy titanium, dimethoxyzirconium dichloride, aluminum isopropoxide Of a composite functional coating film selected from acetoalkoxy aluminum diisopropylate, tin tetrafluoro borate, vanadium oxide, indium-tin oxide, tantalum methoxide, bismuth acetate, dodecyl mercoxide, indium acetylacetonate or mixtures thereof Manufacturing method.
The method of claim 2,

The non-metallic compound is a method for producing a composite functional coating film selected from silicon compounds, fluorine compounds or organic polymer resins.
The method of claim 5,

The silicone compound is 3-aminopropyltriethoxysilane, methyltriethoxysilane, tetraethylorthosilicate, vinyltriethoxysilane, vinylmethyldimethoxysilane, octyltriethoxysilane, phenylgammaaminopropyltrimethoxy Silane, aminonehexyltrimethoxysilane, or mixtures thereof, the fluorine compound being 2-2-bis-4-hydroxyphenylhexafluoropropane, 3,5-bistrifluoromethylaniline, dotecaflo Rho-1-heptanol, 2-4-difluoroaniline, 4-fluorophenylester, dicaprobenzophenone, 2-fluorobiphenyl, tetrafluorohydroquinone or mixtures thereof, the organic polymer Resins are polypropylene, polycarbonate, polyacrylate, polymethylmethacrylate, cellulose acetate, polyvinylchloride, polyurethane, polyester, alkyd resin, epoxy resin, mel The method of Min resins, phenol resins, phenol-modified alkyd resins, epoxy-modified alkyd resins, vinyl-modified alkyd resins, silicone-modified alkyd resins, acrylic melamine resins, polyisocyanate resins, multi-functional coating is selected from epoxy ester resin.
The method of claim 2,

The color expression agent is a method for producing a composite functional coating film selected from zirconium octanoic acid, calcium naphthenate, tetrabutoxy titanium, 3-aminopropyltriethoxysilane, acetoalkoxy aluminum diisopropylate or polyurethane resin.
The method of claim 1,

The composite functional coating solution may be at least one selected from a solvent, a stabilizer, a dispersant, a binder resin, a reducing agent, a surfactant, a wetting agent, a thixotropic agent, or a leveling agent. Method of manufacturing a composite function coating film further comprising.
The method of claim 8,

The solvent is at least one selected from water, alcohol, glycol, acetate, ether, ketone, aliphatic hydrocarbon, aromatic hydrocarbon halogenated hydrocarbon solvents.
The method of claim 1,

The substrate may be powder, flake, bead, ball, fiber, film, sheet, chip, rod, wire A method for producing a composite functional coating film having a shape selected from a wire and a whisker.
The method of claim 1,

Method of producing a composite functional coating film further performing the drying, firing or drying and baking step after the coating.
The method of claim 11,

The drying is 80 to 200 ℃, firing is a method for producing a composite function coating film is carried out at a temperature range of 300 to 700 ℃.
A composite function coating film prepared by the method of any one of claims 1 to 12.
A silver complex compound prepared by reacting a silver compound represented by Formula 1 with an ammonium carbamate compound of Formula 2, an ammonium carbonate compound of Formula 3, an ammonium bicarbonate compound of Formula 4, or a mixture thereof; And

A composite functional coating liquid composition containing a color expressing agent selected from metal compounds, nonmetal compounds or mixtures thereof.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[In the above formula,

X is from oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, carboxylate and derivatives thereof Is a substituent selected,

n is an integer of 1~4, R 1 to R 6 are independently hydrogen, hydroxy, C 1 -C 30 alkoxy, C 1 -C 30 alkyl, C 3 -C 30 in the cycloalkyl, C 6 to each other -C 20 aryl, (C 6 -C 20 ) ar (C 1 -C 30 ) alkyl, functional substituted C 1 -C 30 alkyl, C 6 -C 20 aryl, heterocyclic compound, high molecular compound or Derivative thereof, and R 1 to R 6 may include a hetero element selected from N, S and O in the carbon chain when the functional group is a substituted or unsubstituted alkyl group or aralkyl group, and R 1 and R 2 or R 4 And R 5 may be independently connected to each other to C 1 -C 10 alkylene with or without a hetero atom to form a ring.]
The method of claim 14,

The color expression agent is a composite function coating liquid composition containing 0.01 to 30% by weight based on the total weight of the total composition.
The method of claim 14,

The metal compound is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, As, Se, Eu, Sm, A composite functional coating liquid composition selected from a metal precursor, a metal organic acid salt, or a metal oxide comprising at least one metal selected from Th, Ac, Ce, and Pr.
The method of claim 14,

The non-metallic compound is a composite functional coating liquid composition selected from silicon compounds, fluorine compounds or organic polymer resin.
The method of claim 15,

The color expression agent is a composite functional coating liquid composition selected from octanoic acid zirconium, calcium naphthenate, tetrabutoxy titanium, 3-aminopropyltriethoxysilane, acetoalkoxy aluminum diisopropylate or polyurethane resin.