KR101919978B1 - Method for manufacturing ceramic ink or ceramic pigment using carbamate precursor and ceramic ink or ceramic pigment manufactured by the same - Google Patents
Method for manufacturing ceramic ink or ceramic pigment using carbamate precursor and ceramic ink or ceramic pigment manufactured by the same Download PDFInfo
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- KR101919978B1 KR101919978B1 KR1020150106909A KR20150106909A KR101919978B1 KR 101919978 B1 KR101919978 B1 KR 101919978B1 KR 1020150106909 A KR1020150106909 A KR 1020150106909A KR 20150106909 A KR20150106909 A KR 20150106909A KR 101919978 B1 KR101919978 B1 KR 101919978B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
Abstract
The present invention relates to a process for producing ceramic inks or ceramic pigments using zinc oxide carbamate precursors and metal carbamate precursors, and to ceramic inks or ceramic pigments produced thereby.
Description
The present invention relates to a process for producing ceramic inks or ceramic pigments using carbamate precursors and ceramic inks or ceramic pigments produced thereby and more particularly to a process for producing ceramic inks or ceramic pigments using ceramic ink or ceramic pigments using zinc oxide carbamate precursors and metal carbamate precursors Or a ceramic pigment and a ceramic ink or ceramic pigment produced thereby.
Pure zinc oxide (ZnO) is an electrically and optically attracting material because it can easily improve the conductivity by the addition of impurities. In particular, it is attracting attention as a next-generation process technology that can drive a TFT substrate as a material of an oxide semiconductor, which is attracting attention as a next generation technology, and can realize a very large LCD panel.
And as a precursor for synthesizing the zinc oxide zinc acetate it is the most widely used, in addition to zinc hydroxide, zinc carbonate, zinc carboxylate, zinc nitrate hexahydrate, 2 zinc acetylacetonate hydrate (zinc acetylacetone (Zn (acac) ) hydrate, zinc chloride, and an organometallic compound (Zn (C 6 H 11 ) 2 ) are also used. However, when these precursors are used to synthesize zinc oxide, methods such as chemical vapor deposition (CVD) and pulsed laser deposition are used, and these methods are expensive to manufacture, And the need for such a system.
In order to overcome this problem, Korean Patent Application No. 2013-0136180 discloses that when zinc oxide nanoparticles are synthesized, zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) are added as precursors and reacted at a low temperature (90 ° C) However, in order to overcome such disadvantages, a simple method capable of synthesizing zinc oxide at a low temperature is required in order to overcome such disadvantages do.
In recent years, the demand of consumers for the shortening of the product cycle, various design, quality excellence and low price in the market of ceramics, glass, and tiles is increasing. Especially, the consumer purchase pattern has become more important in terms of function and emotion, and the demand for technology development for ceramics, glass, sanitary ceramics and tiles using digital technology has increased. The application of inkjet printing systems in the fields of ceramics and tiles has many advantages. First, since the design is transmitted as a digital file and patterned, various products can be produced even under mass production. Compared with the existing silk printing process, it is possible to manufacture a single step with various colors. Therefore, the process time is shortened and all colors can be realized with digital four-color (cyan, magenta, yellow and black) ceramic ink. Second, it is an eco-friendly process. The ink is ejected to a desired position to form an image, which results in an ink efficiency of 95% or more. In addition, it is possible to construct a network-based manufacturing site, thereby increasing process efficiency and minimizing facility space. The third is that it is possible to use various materials in a non-contact manner. Since a very small ink droplet is ejected at a predetermined distance from the substrate, it is possible to utilize a substrate that is not flat. In particular, printing can be performed up to the edge of the printing surface, thereby eliminating the need for additional processing such as polishing .
As mentioned above, currently, original technology for inkjet printing equipment and materials related to ceramics, tiles, and the like has been actively secured worldwide, and in Korea, localization of inkjet printing system and industrialization of the four primary colors (CMYK) The source technology for solidified color ceramic ink has been secured.
There are three methods for the synthesis of ceramic inks.
First, a ceramic pigment prepared by firing by a solid reaction method is subjected to physical pulverization to prepare a nano-sized pigment and dispersed using a stabilizer to prepare a ceramic nano-pigment dispersion ink. This is to produce nanoparticles by mass-producing ceramic pigments through a solid reaction and then reducing the original size continuously by pulverization by mechanical synthesis method. This process involves the synthesis of high purity particles by the incorporation of impurities in the process It is difficult to form uniform particles of nanometer size in large quantities. Actually, laser ablation method and high energy ball milling method are used. In the laser ablation method, a laser beam is applied to a raw material in a vacuum to condense vapor of atoms or molecules generated, High-energy ball milling method which is mechanically sharpened to produce nanoparticles requires a high level of technology and is very difficult to manufacture. , There is a problem that an expensive manufacturing facility is required. Ceramic pigments have a very high hardness, which is less than microns but forms hundreds of nano-sized particles by physical grinding. Even if these are dispersed by the surface treatment, the specific gravity is large and the dispersion is unstable, and the phenomenon of precipitation occurs. In order to prevent such precipitation, a high viscosity solvent may be used, and a process of heating the cartridge for ink ejection may be included.
Second, to improve the difficulty of producing such nanoparticles, the metal precursor of the ceramic pigment is chemically treated to prepare nanoparticles. The chemical synthesis method is classified into vapor phase method and liquid phase method. In vapor phase method, expensive equipment is required using plasma or gas evaporation method. Therefore, liquid phase method which can synthesize uniform particles at low cost is widely used. The liquid phase method has the advantage that the reaction speed is fast and the reaction control can be performed at the time of synthesis. The sol-gel method, the hydrothermal synthesis method, the precipitation method, the emulsion method and the thermal decomposition method are known as the kinds of the particle production process using the chemical reaction. These methods enable the desired nanoparticles to be obtained by designing chemical reactions on a nanoscale atom or molecule basis. Thus, although particles of 100 nm or less are formed and dispersed to be applied as nano ink, much research is required for mass production.
Third, the precursor of the metal oxides forming the coloring is dissolved in a certain solvent in accordance with the composition of the ceramic pigment element, and the precursor solution is used as an ink, and the pattern is printed with an inkjet printer to perform coloring by firing. If the metal precursor is decomposed at low temperatures, nanoparticles can be formed at that temperature and color fading due to their fusion can be expected.
Various kinds of precursors of metals or metal oxides which can form ceramic pigments are known. For example, inorganic anions such as chlorine, nitric acid, sulfuric acid, carbonic acid and perchloric acid are well soluble in aqueous solution but insoluble in organic solvent and require high temperature for decomposition of anion upon firing.
On the other hand, organic and chelate anions such as carboxylic acid, oxalic acid, acetylacetone, and alkyl acetylacetic acid are partly dissolved in an organic solvent and decomposed at low temperature and applied. However, since the metals required for the ceramic ink have various oxidized water, the organic metal salts reacted with the metals having a large oxidation number are mostly insoluble in the organic solvent.
Accordingly, an organic anion which can be easily dissolved in polar and nonpolar organic solvents and easily synthesized is required in order to form a stable salt by acting as an anion of various metals .
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a process for producing a carbamate precursor of zinc oxide by mixing zinc carbide precursor and metal carbamate precursor to achieve a reaction time (120-150 ° C) 5 to 30 hours) or a spherical uniform zinc oxide particle prepared by adding a stabilizer to the zinc oxide precursor. The present invention also provides a method for producing a ceramic ink.
It is another object of the present invention to provide a process for producing a ceramic pigment by adding a step of removing and firing a solvent in the process for producing a ceramic ink according to the present invention.
The ceramic ink according to the present invention aims to provide a ceramic ink which can be stably produced at a low temperature for a short time.
The ceramic pigment according to the present invention is intended to provide a ceramic pigment obtained by drying and firing a ceramic ink according to the present invention.
In order to achieve the above object, a method of manufacturing a ceramic ink using a carbamate precursor according to the present invention may include the following steps:
Preparing a carbamate precursor of zinc oxide;
Preparing a metal carbamate precursor; And
Mixing the carbamate precursor of zinc oxide and the metal carbamate precursor obtained above to prepare a ceramic ink.
According to one embodiment of the method for producing a ceramic ink according to the present invention, the carbamate precursor of zinc oxide may be prepared by pyrolyzing zinc carbamate.
The carbamate precursor of zinc oxide may be prepared by dissolving ammonium carbamate in a non-polar solvent, dissolving the zinc salt in a polar solvent, and then mixing the ammonium carbamate and zinc salt dissolved in each of the solvents.
The carbamate precursor of zinc oxide may be prepared by synthesizing a phase transfer reaction of ammonium carbamate dissolved in the nonpolar solvent and a zinc salt dissolved in a polar solvent.
The zinc salt may be at least one member selected from the group consisting of zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc phosphate, zinc fluoride, zinc bromide and zinc iodide.
The carbamate precursor of zinc oxide is selected from the group consisting of one kind selected from zinc (II) di (isobutyl carbamate) and zinc (II) 2-ethylhexylcarbamate, and zinc (II) di (2-ethylhexylcarbamate) Or more.
The metal carbamate precursor may be prepared by reacting a metal precursor with an ammonium carbamate.
The metal carbamate precursor may be prepared by dissolving a metal precursor in a polar solvent, dissolving ammonium carbamate in a non-polar solvent, and then reacting the metal precursor dissolved in each solvent with ammonium carbamate.
The metal precursor may be at least one selected from the group consisting of copper oxide, zinc oxide, vanadium oxide, nickel sulfide, palladium chloride, copper carbonate, iron chloride, gold chloride, nickel chloride, cobalt chloride, bismuth nitrate, acetylacetonated vanadium, cobalt acetate, There may be mentioned manganese, gold acetate, palladium oxalate, copper 2-ethylhexanoate, iron stearate, nickel formate, ammonium molybdate, zinc citrate, bismuth acetate, copper cyanide, cobalt carbonate, chloroplatinic acid chloride, tetrabutoxy titanium, Or a salt or hydrate of metals comprising tin tetrafluoroborate, tantalum methoxide, dodecylmercaptocarbonate, and indium acetylacetonate can be used.
Wherein the ammonium carbamate is selected from the group consisting of ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t- , 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, di Butylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecyl carbamate, hexamethyleneimine ammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridinium ethyl hexyl carbamate, Triethylenediamine isopropyl carbamate, benzylammonium benzyl carbamate, and triethoxysilylpropylammonium triethoxysilylpropyl It is selected from the group consisting of a carbamate can be more than one kinds.
The metal carbamate precursor may be selected from the group consisting of bismuth (III) 2-ethylhexylcarbamate, bismuth (III) tri (2-ethylhexylcarbamate), nickel (II) 2- ethylhexylcarbamate, nickel Ethylhexylcarbamate), iron (III) 2-ethylhexylcarbamate, cobalt (II) 2-ethylhexylcarbamate, cobalt Carbamate, and aluminum (III) tri (2-ethylhexylcarbamate).
The polar solvent is at least one selected from the group consisting of ethanol, methanol, acetone and water,
The nonpolar solvent is selected from the group consisting of alkane solvents such as hexane, heptane, octane, decane and cyclohexane, aromatic alkanes such as benzene, toluene, xylene, anisole, and acetates of chloroform, methylene chloride, ethyl acetate, ethylene glycol and diethylene glycol Monoalkyl ethers, and the like.
The method for preparing zinc oxide nanoparticles for ceramic ink according to the present invention may include the following steps.
Preparing a carbamate precursor of zinc oxide; And
Adding a stabilizer to the carbamate precursor of zinc oxide.
The stabilizer may be oleic acid.
The process for producing ceramic pigments according to the present invention may comprise the following steps:
Preparing a carbamate precursor of zinc oxide;
Preparing a metal carbamate precursor; And
Mixing the carbamate precursor and metal carbamate precursor of the zinc oxide obtained above.
In the above-mentioned method of producing a ceramic pigment,
Removing the solvent of the mixed precursor solution; And
Baking the solvent-removed precursor to produce a ceramic pigment;
As shown in FIG.
The firing step may include a first firing step at 100 ° C to 500 ° C and a second firing step at 500 ° C to 1500 ° C.
The ceramic ink according to the present invention can be produced by the method for producing a ceramic ink according to the present invention.
The ceramic pigments according to the present invention can be produced by the process for producing ceramic pigments according to the present invention.
According to the production method of the ceramic ink or ceramic pigment of the present invention, a ceramic ink or pigment can be produced at a low temperature (120 to 150 ° C) for a short reaction time (5 to 30 hours).
1 is a graph showing FT-IR and 1 H, 13 C NMR spectra of the structures of synthesized IBA-IBC and Zn (IBC) 2 .
FIG. 2 is a graph showing the results of thermal analysis of Zn (IBC) 2 according to a heating rate per minute, wherein FIG. 2A is a TGA and FIG. 2B is a graph using DSC.
3 is a graph showing the UV-vis absorption spectrum of the zinc oxide nanoparticle colloid solution obtained when oleic acid concentration was used as a stabilizer at 10%, 20% and 30%.
4 (a) is a TEM photograph of zinc oxide nanoparticles prepared at a concentration of 10% oleic acid, 4 (b) is oleic acid concentration of 20% and 4 (c) is oleic acid concentration of 30% (b) is a photograph of an SEM with an oleic acid concentration of 10%, and (e) is an HR-TEM photograph of an oleic acid concentration of 10%.
5 is a graph showing an XRD pattern of zinc oxide nanoparticles prepared by pyrolyzing Zn (IBC) 2 at 125 ° C.
6A is a graph showing an XRD pattern of Example 7. FIG.
6B is a graph showing an XRD pattern of the eighth embodiment.
6C is a graph showing an XRD pattern of Example 9. Fig.
FIG. 6D is a graph showing an XRD pattern of Example 10. FIG.
FIG. 6E is a graph showing the XRD pattern of Example 11. FIG.
FIG. 6F is a graph showing the XRD pattern of Example 12. FIG.
7 is a photograph and a graph showing the SEM shape and EDX analysis of the ceramic pigment of Example 7. Fig.
8 is a photograph and a graph showing the SEM shape and EDX analysis of the ceramic pigment of Example 8. Fig.
9 is a photograph and a graph showing the SEM shape and EDX analysis of the ceramic pigment of Example 9. Fig.
10 is a photograph and a graph showing the SEM shape and EDX analysis of the ceramic pigment of Example 10. Fig.
11 is a photograph and a graph showing the SEM shape and EDX analysis of the ceramic pigment of Example 11. Fig.
12 is a photograph and a graph showing the SEM shape and EDX analysis of the ceramic pigment of Example 12. Fig.
13 is a graph showing an XRD pattern of a Bi / Zn-based pigment.
14 is a graph showing an XRD pattern of a Ni / Zn-based pigment.
15 is a graph showing an XRD pattern of a Co / Zn-based pigment.
16 is a graph showing an XRD pattern of Fe / Zn-based pigment.
17 is a graph showing an XRD pattern of Ni / Zn / Si-based pigment.
18 is a graph showing an XRD pattern of a Co-Al-Zn based pigment.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.
Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.
Hereinafter, a method for producing a ceramic ink using the carbamate precursor according to the present invention and a ceramic ink produced by the method will be described in detail.
A method of manufacturing a ceramic ink according to an embodiment of the present invention is characterized by comprising the following steps:
Preparing a carbamate precursor of zinc oxide;
Preparing a metal carbamate precursor; And
Mixing the carbamate precursor of zinc oxide and the metal carbamate precursor obtained above to prepare a ceramic ink.
The carbamate precursor of zinc oxide may be prepared by pyrolyzing zinc carbamate. One embodiment of the pyrolysis reaction formula is as follows.
Zn (OCONHC4H9)2+ H2O → zinc oxide + 2C4H9NH2 +2 CO2
The reaction formula shows a thermal decomposition reaction of zinc carbamate. As shown in the above reaction formula, zinc carbamate undergoes thermal decomposition to produce zinc oxide. At this time, the decomposition of CO2And isobutylcarbamic acid produced by the reaction of isobutylamine stabilize zinc oxide. When zinc carbamate is used as a precursor of zinc oxide, there is an advantage in that spherical uniform zinc oxide particles can be produced at a low temperature of 150 캜 or lower while overcoming the disadvantage of requiring a long reaction time in the past.
In the step of producing the carbamate precursor of zinc oxide of the production method of the ceramic ink according to the present invention, zinc oxide nanoparticles can be prepared by further comprising stabilizers.
The carbamate precursor of zinc oxide may be prepared by dissolving ammonium carbamate in a nonpolar solvent, dissolving a zinc salt in a polar solvent, and then mixing the ammonium carbamate and zinc salt dissolved in each of the solvents .
The carbamate precursor of zinc oxide may be prepared by synthesizing a phase transfer reaction of ammonium carbamate dissolved in the nonpolar solvent and a zinc salt dissolved in a polar solvent.
The zinc salt is not particularly limited and is preferably at least one selected from the group consisting of zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc phosphate, zinc fluoride, zinc bromide and zinc iodide, Zinc chloride, zinc nitrate and zinc sulfate are more preferable.
The ammonium carbamate is not particularly limited and includes, for example, ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butyl ammonium n-butyl carbamate, isobutyl ammonium isobutyl carbamate, butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate (EHAEHC), octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2- Nonoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneimine carbamate, morpholinium Triethylenediamine isopropylcarbamate, benzylammonium benzyl carbamate, and triethoxysilyl triethoxysilylmethylsulfate. Be at least one profile in the tree is selected from ammonium propyl silyl ethoxy group consisting of carbamate, and the 2-ethylhexyl 2-ethylhexyl ammonium carbamate is most preferred.
The polar solvent is at least one selected from the group consisting of ethanol, methanol, acetone and water,
The nonpolar solvent is selected from the group consisting of alkane solvents such as hexane, heptane, octane, decane and cyclohexane, aromatic alkanes such as benzene, toluene, xylene, anisole, and acetates of chloroform, methylene chloride, ethyl acetate, ethylene glycol and diethylene glycol Monoalkyl ethers, and the like.
The preparation of the carbamate precursor of zinc oxide proceeds at room temperature, and a magnetic stirrer or homogenizer may be used to accelerate the reaction at the interface.
The preparation of the carbamate precursor of zinc oxide can be synthesized from a water-soluble salt of zinc (hereinafter, also referred to as a zinc salt dissolved in a polar solvent) in the presence of 2-ethylhexylammonium 2-ethylhexylcarbamate have.
That is, the zinc salt dissolved in water and the EHAEHC dissolved in the nonpolar solvent, which are not soluble in water, can be easily produced by an interfacial reaction (phase transfer reaction). The carbamate precursor (carbamate salt) of zinc oxide thus obtained was Zn4(μ4-O) (O2CNHR)6/ RTI > complexes such as < RTI ID = 0.0 > Zn / carbamate < / RTI > Such a complex may also be decomposed at 250 캜 or less in the presence of an alkylamine to produce zinc oxide. This is because the carbamate bond is weakened by the metal bond (Metal-OCONHR) to become close to the covalent bond, that is, in the carbamate (OCONHR), nitrogen (N) attracts electrons, This phenomenon is caused by weakening the bond between the bonds. Therefore, the metal carbamate complex is decomposed at a low temperature.
Specific examples of the zinc oxide carbamate precursor thus obtained include zinc (II) di (isobutyl carbamate), zinc (II) 2-ethylhexylcarbamate and zinc (II) di (2-ethylhexylcarbamate) And the like.
The metal carbamate precursors used in the present invention can be prepared by reacting a metal precursor with an ammonium carbamate.
The metal carbamate precursor may be prepared by dissolving a metal precursor in a polar solvent, dissolving ammonium carbamate in a non-polar solvent, and then reacting the metal precursor dissolved in each solvent with ammonium carbamate.
The metal precursor is not particularly limited and includes, for example, copper oxide, zinc oxide, vanadium oxide, nickel sulfide, palladium chloride, copper carbonate, iron chloride, There is provided a process for producing a cobalt compound which comprises reacting a cobalt compound such as vanadium, cobalt acetate, tin lactate, manganese oxalate, gold acetate, palladium oxalate, copper 2-ethylhexanoate, iron stearate, nickel formate, ammonium molybdate, zinc citrate, bismuth acetate, Is selected from salts or hydrates of metals consisting of titanium tetrachloride, titanium tetrachloride, titanium tetrachloride, tetrabutoxy titanium, dimethoxy zirconium dichloride, aluminum isopropoxide, tin tetrafluoroborate, tantalum methoxide, dodecylmethacrylate gold and indium acetylacetonate It may be more than one kind.
The ammonium carbamate is not particularly limited and includes, for example, ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butyl ammonium n-butyl carbamate, isobutyl ammonium isobutyl carbamate, butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, Mate, pyridinium ethylhexylcarbamate, triethylenediamine isopropyl carbamate, benzylammonium benzyl carbamate, and triethoxysilyl pro One member selected from the group consisting of ethoxy silyl propyl carbamate in the ammonium tree may be equal to or greater than.
The metal carbamate precursor thus obtained may be selected from the group consisting of bismuth (Ⅲ) 2-ethylhexylcarbamate, bismuth (Ⅲ) tri (2-ethylhexylcarbamate), nickel (Ⅱ) 2-ethylhexylcarbamate, nickel (II) di (2-ethylhexylcarbamate), aluminum (III) 2 (ethyl) hexylcarbamate, cobalt -Ethylhexylcarbamate and aluminum (III) tri (2-ethylhexylcarbamate).
The polar solvent is at least one selected from the group consisting of ethanol, methanol, acetone and water,
The nonpolar solvent is selected from the group consisting of alkane solvents such as hexane, heptane, octane, decane and cyclohexane, aromatic alkanes such as benzene, toluene, xylene, anisole, and acetates of chloroform, methylene chloride, ethyl acetate, ethylene glycol and diethylene glycol Monoalkyl ethers, and the like.
The method for preparing zinc oxide nanoparticles for ceramic ink according to the present invention may include the following steps.
Preparing a carbamate precursor of zinc oxide; And
Adding a stabilizer to the carbamate precursor of zinc oxide.
The stabilizer is not particularly limited and may be a fatty acid such as oleic acid.
A method of manufacturing a ceramic pigment according to another embodiment of the present invention may include the following steps:
Preparing a carbamate precursor of zinc oxide;
Preparing a metal carbamate precursor;
Mixing the carbamate precursor and metal carbamate precursor of the zinc oxide obtained above.
In the above-mentioned method of producing a ceramic pigment,
Removing the solvent of the mixed precursor solution; And
And then baking the precursor from which the solvent has been removed to prepare a ceramic pigment.
The firing step may include a first firing step at 100 ° C to 500 ° C and a second firing step at 500 ° C to 1500 ° C.
The temperature of the first sintering step is preferably 100 ° C to 500 ° C. If the temperature is outside the above range, it may be difficult to remove the remaining solvent, which is not preferable.
It is preferable that the temperature of the second firing step is 500 ° C to 1500 ° C. If the temperature is outside the above range, it is difficult to remove the organic anion and the chelated compound, and the crystal is not well grown .
The ceramic pigment may be a metal oxide doped with a transition metal ion or a rare earth metal ion. The oxidation state and coordination number of such dopant metals can determine the color properties of the ceramic pigments. Color is also associated with partially filled d and f block elements. In the present invention, the above metal ions are used as a dopant, zinc oxide as a host is predominant in pigments, and some silica or alumina may act as a cohost.
The 2-ethylhexylammonium 2-ethylhexylcarbamate (EHAEHC) used in the present invention can be obtained by reacting 2-ethylhexylamine and CO2And a slight excess of amine can be used.
The amine may be a C2 to C12 carbon as an achyl amine and is effective when the branch is present at each carbon number. For example, in the case of C3, n-propylamine and isopropylamine are included. C4, there may be mentioned n-butylamine, isobutylamine, tert-butylamine and sec-butylamine. C5, there may be mentioned n-pentylamine, isopentylamine, tert-pentylamine, neopentylamine and sec-pentylamine. The amines belonging to C6-C12 all belong to the above n-, iso-, tert-, neo- and sec-compounds and all isomers of primary amines having carbon numbers from 2 to 10, It belongs to this.
The alkylamine may be a secondary amine in addition to the primary amine, and is effective when the number of carbon atoms of the C2-C12 is varied at each carbon number. For example, in the case of C3, n-propylamine and isopropylamine are included. C4, there may be mentioned n-butylamine, isobutylamine, tert-butylamine and sec-butylamine. C5, there may be mentioned n-pentylamine, isopentylamine, tert-pentylamine, neopentylamine and sec-pentylamine. The amines belonging to C6-C12 all belong to the above-mentioned n-, iso-, tert-, neo- and sec-compounds and the secondary of all the isomers having carbon numbers from 2 to 10, Amin belongs to this.
If the length of carbon is shortened, the solubility of the obtained alkylammonium alkylcarbamate in a non-polar solvent may be reduced. On the other hand, as carbon length increases, solubility increases. However, since the number of carbamates increases as the oxidation number of the resultant metal increases, the content of the metal salt in the solid component constituting the whole ceramic ink component decreases, so that it is necessary to appropriately mix and control.
A ceramic ink or a piece according to the present invention can be produced by a process for producing a ceramic ink or pigment according to the present invention.
Hereinafter, the present invention will be described in detail based on examples and experimental results for demonstrating the superiority of the method for producing ceramic inks of the present invention. However, the following examples are for illustrative purposes only, and the present invention is not limited to the following examples.
Example
<Raw materials>
As a precursor of zinc oxide, Zn (IBC)2(99.8%) and zinc powder (zinc (II)) were used to synthesize isobutylammonium isobutylcabamate (IBA-IBC) powder, purum, > 99%) and 2-methoxyethanol was used as a product of Sigma Aldrich.
Oleic acid was used as a stabilizer to prevent agglomeration of zinc oxide nanoparticles, and Sigma Aldrich was used as a reagent grade.
<Measurement property>
In order to confirm the structure of each synthesized substance,OneH, and13C NMR spectra were used, which were purchased from Bruker,
Fourier Transform-infrared spectroscopy (FT-IR) was analyzed using a 640-IR (Varian, Palo Alto, CA, USA) spectrophotometer.
To determine the size, shape and distribution of zinc oxide nanoparticles, photographs were taken using a filtered energy-filtered transmission electron microscope (120 kV, Carl Zeiss, LIBRA 120) , And one or two drops were dropped on a carbon-coated TEM grid using 2-methoxyethanol as a dispersion solvent for each nanoparticle, followed by drying in an oven at 60 ° C.
The size and shape of the nanoparticles were determined from the obtained TEM photographs, and the interstitial distance of the crystal structure of each nanoparticle was confirmed by HR-TEM (JEM-3010, JEOL).
The UV-vis absorption spectrum was measured by UV-Vis spectrophotometer (Cary 100) and absorbance was measured at 200 to 800 nm. In order to analyze the thermal properties of zinc oxide precursor and zinc oxide, differential scanning calorimetry (DSC) was carried out using Sinco Evo Setaram DSC 131 at a heating rate of 5/10/20 캜 / min in a nitrogen atmosphere, Thermogravimetric analysis (TGA) was measured using a
The x-ray diffraction spectrum of zinc oxide was measured using a Shimadzu XD-D1 X-ray diffractometer at a scan rate of 2 캜 /alphaRay was observed.
Preparation of zinc oxide carbamate precursor
[Preparation Example 1] Synthesis of zinc (II) di (isobutyl carbamate) complex ((Zn (IBC) 2 )
Zn (IBC)2) First, isobutylammonium isobutyl carbamate (IBA-IBC) was synthesized before synthesis. After adding isobutylamine (30 mL) and dry toluene (60 mL) to a 2-necked round bottom flask (250 mL), slowly add CO2 Gas (50 mL / min), and bubbled with stirring for 1 hour. The CO2 After the gas was injected, white powder was immediately formed. After completion of the reaction, the resulting white solid was filtered, washed several times with toluene, and vacuum dried at room temperature.
The results of IBA-IBC analysis are as follows.
FT-IR (KBr, cm-One) 3430 (N-H), 2954-2913 (C-H), 1631-1587 (C = O), 150 (C-O, C-N).
One≪ 1 > H NMR (600 MHz, CDCl33) [delta] 7.61 (s, 3H, -CH2N + H 3 ), 4.43 (s, 1H, -CH2NHCO-), 2.88-2.86 (d, 2H,+NH3CH 2 CH (CH3)2), 2.58 (d, 2H, (CH3)2CHCH 2 NH-), 1.89-1.82 (m, 1H,+NH3CH2CH(CH3)2), 1.68-1.62 (m, 1H, (CH3)2CHCH2NH-), 0.96 (d, 6H,+NH3CH2CH (CH 3 )2-), 0.87 (d, 6H, (CH 3 )2CHCH2NH-).
13C NMR (CDCl33) [delta] 163.6 (-NHCOO-), 49.5 (H3N+ CH2CH (CH3)2), 47.4 ((CH3)2CHCH2NH-), 29.1 (H3N+CH2 CH (CH3)2), 28.4 ((CH3)2 CHCH2NH-), 20.2 (H3N+CH2CH (CH3)2), 20.1 ((CH3)2CHCH2NH-).
The IBA-IBC obtained above (15.3 mmol, 2.91 g) was dissolved in 2-methoxyethanol (25 mL), and 2-methoxyethanol (5 mL) was added to a 1-necked round bottom flask After dispersing the powder (7.6 mmol, 0.50 g), the two solutions were mixed. The mixture was stirred at room temperature for 24 hours until the zinc powder reacted and the reaction mixture became clear. After the reaction was completed, the solvent was evaporated using a rotary evaporator to obtain a white solid (2.26 g, 6.98%). The thus obtained zinc (II) di (isobutyl carbamate (Zn (IBC)2The results of the instrumental analysis are as follows.
FT-IR (KBr, cm-One) 3328.58 (N-H), 2954-2919 (C-H), 1573-1529 (C-O), 1319-1290 (C-O, C-N).One≪ 1 > H NMR (600 MHz, CDCl33) [delta] 4.92 (s, 2H, 2 -CH2-NH-CO-), 2.52-2.51 (d, 4H, 2 (CH3)2CHCH 2NH), 1.73-1.57 (m, 2H, 2 -CH2CH(CH3)2), 0.90-0.87 (d, 12H, 2 (CH 3 )2CHCH 2NH-).13C NMR (CDCl33) [delta] 164.3 ((CH3)2CHCH2NH-CO-O-), 50.2 (2 -NHCH2CH (CH3)2), 31.4 (-NHCH2CH(CH3)2), 29.2 (-NHCH2CH(CH3)2), 20.1 (-NHCH2CH (CH3)2).
[Production Example 2] Synthesis of zinc (II) 2-ethylhexylcarbamate complex
Synthesis of zinc (II) 2-ethylhexylcarbamate 2-ethylhexylammonium 2-ethylhexylcarbamate (EHAEHC) was synthesized.
2-ethylhexylamine (30 mL) and dry methylene chloride (120 mL) were added to a 2-neck round bottom flask (250 mL)2 Gas (50 mL / min) was injected and bubbled with stirring for 1 hour. CO2 After the gas was injected, if no further reaction occurred, the solvent was removed using a rotary evaporator at 40 ° C or lower to obtain a transparent liquid EHAEHC.
Zinc chloride (ZnCl2, 13.61 g, 0.1 mol) was dissolved in distilled water (300 mL), and EHA-EHC (75.63 g, 0.25 mol) was dissolved in hexane (500 mL) using a magnetic stirrer. The zinc chloride solution dissolved in the distilled water was added dropwise to the EHA-EHC solution and mixed. The mixed solution was stirred at 1000 rpm for 1 hour, and the hexane layer was separated and washed with distilled water. The solvent was removed by using a rotary evaporator, and then a transparent and viscous form of zinc (II) 2-ethylhexylcarbamate .
Preparation of metal carbamate precursors
[Preparation Example 3] Preparation of bismuth (Ⅲ) 2-ethylhexylcarbamate complex
Bismuth trichloride (Bi (NO3)3·
[Preparation Example 4] Preparation of nickel (II) 2-ethylhexylcarbamate complex
The synthesis of the nickel (II) 2-ethylhexylcarbamate complex Nickel chloride hydrate (NiCl2·
[Preparation Example 5] Iron (III) 2-ethylhexylcarbamate complex
Chloride iron hydrate (FeCl3·
[Production Example 6] Cobalt (II) 2-ethylhexylcarbamate complex
Cobalt chloride hydrate (CoCl2·
[Preparation Example 7] Synthesis of aluminum (III) 2-ethylhexylcarbamate complex
Aluminum chloride hydrate (AlCl3·
Manufacture of zinc oxide nanoparticles
[Preparation Example 8] Synthesis of zinc oxide nanoparticles by thermal reduction method
As a starting material for preparing zinc oxide (ZnO) nanoparticles, 1.0% of Zn (IBC) of Production Example 1,2 Solution.
A 1-neck round bottom flask was charged with 1.0% Zn (IBC)2Solution (30 mL), 2-propanol / oleic acid = 9/1, 8/2, 7/3 (10 mL) was added and stirred. The temperature in the flask was then raised from 80 DEG C to 125 DEG C and maintained at this temperature for 1 hour. As the reaction progressed, the color of the clear solution changed to white indicating the formation of zinc oxide nanoparticles. The reaction solution was cooled at 20 ° C and zinc oxide nanoparticles were collected using a centrifuge. The collected zinc oxide nanoparticles were washed three times with 2-methoxyethanol and dried under vacuum. Various zinc oxide nanoparticles were produced in the same manner by varying the amount of the stabilizer during the synthesis. The results are shown in Table 1. The obtained zinc oxide nanoparticles are shown in FIGS. 4 (a) to 4 (c) 4 (d) and HR-TEM photographs are shown in SEM and Fig. 4 (e).
[Preparation Example 9] Synthesis of zinc oxide nanoparticles
The starting material was prepared in the same manner as in Preparation Example 8, except that the zinc (II) 2-ethylhexylcarbamate complex obtained in Preparation Example 2 was used.
Manufacture of ceramic ink
[Example 1] Production of Bi / Zn-based ceramic ink
Ethylhexylcarbamate complex (92 mmol) of Preparation Example 2 and bismuth (Ⅲ) 2-ethylhexylcarbamate complex (16 mmol) of Preparation Example 3 were dissolved in hexane (200 ml) with a
[Example 2] Production of Ni / Zn-based ceramic ink
Ethylhexylcarbamate complex (46.86 g, 99.5 mmol) of Preparation Example 2 and the nickel (II) 2-ethylhexylcarbamate complex of Preparation 4 (2.44 g, 5.0 mmol) were dissolved in hexane ) Was stirred for 30 minutes at 1000 rpm to prepare a yellow green ceramic ink consisting of a mixed carbamate complex of zinc (II) / nickel (II) 2-ethylhexylcarbamate, The results are shown in Table 1.
[Example 2-1] Production of Ni / Zn-based ceramic ink
Zinc chloride (ZnCl2, 13.55 g, 95 mmol) and nickel chloride hydrate (NiCl2·
[Example 3] Production of Fe / Zn-based ceramic ink
Ethylhexylcarbamate complex (23.36 g, 50 mmol) of Preparation Example 2 and the iron (III) 2-ethylhexylcarbamate complex of Preparation 5 (23.27 g, 50 mmol) were dissolved in hexane ) For 3 minutes with a paste mixer at 1500 rpm to prepare a brown ceramic ink comprising a mixed carbamate complex of zinc (II) / iron (III) 2-ethylhexylcarbamate. The results are shown in Table 1 Respectively.
[Example 3-1] Production of Fe / Zn-based ceramic ink
Zinc chloride (ZnCl2, 6.87 g, 50 mmol) and ferrous chloride hydrate (FeCl3·
[Example 4] Production of Co / Zn-based ceramic ink
Ethylhexylcarbamate complex (42.05 g, 90 mol) of Preparation Example 2 and the cobalt (II) 2-ethylhexylcarbamate complex of Preparation 6 (4.21 g, 10 mmol) were dissolved in
[Example 4-1] Production of Co / Zn-based ceramic ink
Zinc chloride (ZnCl2, 12.25 g, 90 mmol) and cobalt chloride hydrate (CoCl2· 6H2EHA-EHC (75.63 g, 0.25 mol) was dissolved in hexane (300 mL) using a magnetic stirrer. The two metal precursors were dissolved in distilled water (300 mL). A solution prepared by dissolving the two metal precursors was added dropwise to the EHA-EHC solution. The mixed solution was stirred at 1000 rpm for 1 hour, and the hexane layer was separated and washed with distilled water three times. Then, a mixed green color consisting of a mixed carbamate complex of violet zinc (II) / cobalt (II) 2-ethylhexylcarbamate Ceramic ink.
[Example 5] Production of Ni / Zn-Si based ceramic ink
Ethylhexylcarbamate complex (44.38 g, 95 mmol) of Preparation Example 2, nickel (II) 2-ethylhexylcarbamate complex of Preparation 4 (2.45 g, 5 mmol), tetraethylortho Silicate (Si (OC2H5)4, 20.83 g, and 0.1 mol) were dissolved in hexane (200 mL) with stirring in a paste mixer at 1500 rpm for 3 minutes to prepare a solution of zinc (II) / nickel (II) 2-ethylhexylcarbamate / Si complex cyan ceramic And the results are shown in Table 1. < tb > < TABLE >
[Example 5-1] Production of Ni / Zn-Si based ceramic ink
Zinc chloride (ZnCl2, 12.93 g, 95 mmol) and nickel chloride hydrate (NiCl2·
[Example 6] Production of Co / Zn / Al-based ceramic ink
Ethylhexylcarbamate complex (11.68 g, 25 mmol) of Preparation Example 2 and the cobalt (II) 2-ethylhexylcarbamate complex of Preparation 5 (10.53 g, 25 mmol) Aluminum (III) 2-ethylhexylcarbamate (33.73 g, 100 mmol) was uniformly dissolved in hexane (200 mL) with stirring using a paste mixer at 1500 rpm for 10 minutes to obtain cobalt (II) / zinc (II) ) 2-ethylhexylcarbamate complex blue-based ceramic ink was prepared, and the results are shown in Table 1.
[Example 6-1] Blue system
Zinc nitrate (Zn (NO)2· 6H2O, 7.44 g, 25 mmol) and cobalt chloride hydrate (CoCl2·
Manufacture of ceramic pigments
[Example 7] Preparation of Yellow Ceramic Pigment
The solvent of the yellow ceramic ink (100 mL) composed of the mixed carbamate complex of zinc (II) / bismuth (III) 2-ethylhexylcarbamate obtained in Example 1 was removed using a rotary evaporator, and the mixture was put into a crucible , The temperature was raised at a firing rate of 5 ° C / min in a furnace. In the calcination step, the calcination proceeds at 300 ° C to remove the residual solvent. In the second calcination, the organic anion and the chelated compound are removed, and the calcination temperature is elevated to 600 ° C for 2 hours. Finally, yellow (L * 86.2, a * 0.96, b * 49.8) ceramic pigments were obtained and the results are shown in Table 1.
[Example 8] Production of green-brown ceramic pigment
The solvent of the greenish brown ceramic ink (100 mL) consisting of the mixed carbamate complex of zinc (II) / nickel (II) 2-ethylhexylcarbamate of Example 2 was removed and placed in a crucible. Lt; / RTI > The calcination step was carried out at 300 DEG C to remove the residual solvent and the organic chelate part, and the second calcination was carried out by raising the temperature to 1000 DEG C and holding for 1 hour. Finally, ceramic pigments having a light green color (L * 63.4, a * -2.3, b * 40.9) were obtained, and the results are shown in Table 1.
[Example 9] Preparation of Brown Ceramic Pigment
A paste-type pigment precursor obtained by removing the solvent of a brown ceramic ink (100 mL) composed of a mixed carbamate complex of zinc (II) / iron (III) 2-ethylhexylcarbamate of Example 3 was placed in a crucible, Lt; RTI ID = 0.0 > 5 C / min. ≪ / RTI > The calcination was carried out at 300 DEG C to remove the residual solvent and the organic chelate component, and the second calcination was continued for 1 hour while raising the temperature to 1000 DEG C. [ Finally, a brown (L * 38.9, a * 19.5, b * 21.5) ceramic pigment was obtained.
[Example 10] Green ceramic pigment
The solvent of the green ceramic ink (100 mL) consisting of the mixed carbamate complex of zinc (II) / cobalt (II) 2-ethylhexylcarbamate of Example 4 was removed and the resulting mixed pigment precursor in paste form was placed in a crucible , And the furnace was heated at a firing rate of 5 DEG C / min. The calcination step was carried out at 300 DEG C to remove residual solvent and organic chelating agent, and the second calcination was continued for 1 hour at 1000 DEG C with increasing calcination temperature. Finally, green (L * 25.6, a * -17.1, b * 4.4) ceramic pigments were obtained.
[Example 11] Cyan green ceramic pigment
A paste-like mixed precursor obtained by removing the solvent of the zinc (II) / nickel (II) 2-ethylhexylcarbamate / Si complex ceramic ink (100 mL) of Example 5 using a rotary evaporator was placed in a crucible, Lt; RTI ID = 0.0 > 5 C / min. ≪ / RTI > In the sintering step, the remaining solvent was removed by proceeding plasticity at 300 ° C, and the sintering temperature was raised to 1000 ° C for the second sintering and maintained for 1 hour. Finally, a cyan (L * 63.0, a * -9.57, b * -16.4) ceramic pigment was obtained.
[Example 12] A blue ceramic pigment
A paste-like mixed precursor obtained by removing the solvent of cobalt (II) / zinc (II) / Al (III) 2-ethylhexylcarbamate complex ceramic ink (100 mL) of Example 6 was placed in a crucible, And the temperature was raised at a firing rate of 5 DEG C / min. In the sintering step, the remaining solvent was removed by progressing plasticity at 300 DEG C, and the sintering temperature was raised to 1000 DEG C for the second sintering, and the sintering was continued for 1 hour. Finally, blue (L * 31.7, a * 7.1, b * -38.9) ceramic pigments were obtained.
Manufacture of ceramic ink using zinc oxide nanoparticles
[Example 13] Production of Bi / Zn-based ceramic ink
The zinc oxide nanoparticles (92 mmol) obtained in Preparation Example 9 and the bismuth (III) 2-ethylhexylcarbamate complex (16 mmol) of Preparation Example 3 were stirred in hexane (200 mL) at 1500 rpm for 3 minutes using a paste mixer A yellow ceramic ink comprising a mixed carbamate complex of bismuth (Ⅲ) and zinc (Ⅱ) 2-ethylhexylcarbamate was prepared and the results are shown in Table 1.
Preparation of Ceramic Pigment Using Zinc Oxide Nanoparticles
[Example 14] Preparation of Yellow Ceramic Pigment
The solvent of the yellow ceramic ink (100 mL) composed of the mixed carbamate complex of zinc (II) / bismuth (III) 2-ethylhexylcarbamate obtained in Example 13 was removed using a rotary evaporator, and the mixture was put into a crucible , The temperature was raised at a firing rate of 5 ° C / min in a furnace. In the calcination step, the calcination proceeds at 300 ° C to remove the residual solvent. In the second calcination, the organic anion and the chelated compound are removed, and the calcination temperature is elevated to 600 ° C for 2 hours. Finally, yellow (L * 86.2, a * 0.96, b * 49.8) ceramic pigments were obtained and the results are shown in Table 1.
<Measurement and Results>
IBA-IBC, Zn (IBC), < RTI ID = 0.0 >2 And zinc oxide nanoparticles are as follows.
Structure analysis of IBA-IBC and Zn (IBC) 2
To synthesize a precursor of zinc oxide, carbon dioxide (CO2) And isobutylamine, CO2Isobutylammonium isobutyl carbamate (IBA-IBC) was synthesized by gas bubbling method. Fig. 1 is a graph showing the relationship between the synthesized IBA-IBC and Zn (IBC)2The structure of FT-IR andOne1 H NMR and13C NMR spectrum. 1 (a) shows IBA-IBC and Zn (IBC)2≪ / RTI > As shown in Fig. 1 (a), the characteristic absorption of IBA-IBC is about 3430, 1631, 1587, 1050 cm-One (IBC), which corresponds to the stretching vibration of N-H, C = O, and C-N bonds of each carbamate group,2Lt; RTI ID = 0.0 > 3328, 1573-1529, 1319-1290 cm-One The absorption band corresponding to stretching vibration of N-H, C = O, C-N bonds was confirmed.
1 (b)OneAs shown in the 1 H NMR spectrum, in the NMR spectrum of IBA-IBC, the peaks of the methyl, methine and methylene hydrocarbons of the carbamate group were 0.87, 1.62-1.68 and 2.58 ppm, respectively, While the isobutyl group hydrogen of the ammonium salt showed a slight peak shift in the lower field.
In FIG. 1 (c), the peak of the carbon atom of IBA-IBC was observed at 20.1, 20.2, 28.4, 29.1, 47.4, 49.5 and 163.0 ppm, and the carbon atom peak of the carbonyl group was observed at 163 ppm.
Zinc (II) isobutyl carbamate (Zn (IBC)2) Was synthesized using the reaction of IBA-IBC with zinc powder as shown in the following formula (1). As the reaction proceeded for 24 hours, Zn (IBC)2The reaction mixture changed from a gray solution to a clear solution. Zn (IBC)2Was confirmed through the NMR spectrum of FIG. 1 (b).
As shown in Fig. 1 (d), the peaks of methyl, methine and methylene hydrogen were 0.86 to 0.96 ppm, 1.65 to 1.85 ppm, and 2.58 to 2.87 ppm, respectively. 1 (e)13It was confirmed that a peak appeared at 164.3 ppm due to the carbonyl group (C = O) of the carbamate group in the C NMR spectrum.
[Chemical Formula 1]
(A) TGA and (b) DSC analysis according to the heating rate of Zn (IBC) 2 per minute
2 (a) and 2 (b) illustrate the use of TGA and DSC for Zn (IBC)2FIG. The TGA and DSC were measured at 5, 10, and 20 ℃ / min, respectively, and the thermal decomposition temperature was decreased as the heating rate per minute decreased. Especially, the thermogravimetric analysis showed that the heating rate per minute significantly affected the decomposition temperature. Therefore, Zn (IBC)2It is found that a suitable reaction time is required for pyrolysis.
2 (b), the endothermic peaks at about 153 and 158 ° C in the DSC graph are Zn (IBC)2Is decomposed into zinc oxide, carbon dioxide and isobutylamine by heat, and an exothermic peak appearing at about 323 ° C is caused by agglomeration of the formed zinc oxide nanoparticles, so that no change in weight was observed in the thermogravimetric analysis . As in the TGA analysis graph, the DSC analysis graph also confirmed the effect of the temperature rise rate per minute. When the rate of temperature increase per minute was 20 ° C / min, the endothermic peak appeared at 171 ° C. However, when the rate of temperature increase per minute was 5 ° C / It can be seen that an endothermic peak appears in the vicinity.
In the TGA graph of FIG. 2 (a), a mass loss of 81% was observed up to 150 ° C., and mass loss was not observed in the temperature range of 150 to 500 ° C. The total mass loss was 81% and the zinc oxide content was 19% by TGA.
The formation of zinc oxide can be explained as follows. That is, Zn (IBC)2Can be decomposed while forming zinc oxide by simple heat treatment within a range of 120 to 150 ° C, and Zn (IBC)2Is decomposed by the following equation.
Zn (OCONHC4H9)2+ H2O → zinc oxide + 2 C4H9NH2 +2 CO2
The equation is Zn (IBC)2Indicates decomposition into isobutylamine and carbon dioxide while forming zinc oxide simply by heat.
Effect of Oleic Acid Concentration on the Formation of Zinc Oxide Nanoparticles
Fig. 3 shows the UV-vis absorption spectrum of the zinc oxide nanoparticle colloid solution obtained when oleic acid was used as a stabilizer. Absorption peaks of all samples were observed between 370 and 400 nm, and no peaks were observed except for the peak of zinc oxide nanoparticles in the spectrum. The zinc oxide nanoparticles stabilized with oleic acid exhibited a strong maximum absorption peak at about 351 nm, which means that the size of the zinc oxide nanoparticles decreased and absorption took place in the lower wavelength spectrum.
FIG. 4 shows TEM, SEM and HR-TEM photographs of zinc oxide nanoparticles prepared by varying the concentration of oleic acid. As shown in the TEM photographs of FIGS. 4 (a) to 4 (c), when the concentration of oleic acid was adjusted to 10, 20 and 30% in order to control the shape of the zinc oxide nanoparticles, It was confirmed that the zinc oxide nanoparticles were well formed as spherical nanoparticles, unlike the case of using polyvinylpyrrolidone (PVP). In addition, when 10% oleic acid was used, zinc oxide nanoparticles having the smallest and uniform size were formed. As a result, when the stabilizer was added in excess, the stabilizers coagulated with each other, Respectively. In the SEM image of FIG. 4 (d), it was confirmed that spherical zinc oxide nanoparticles having a diameter of 20 to 50 nm were formed. This confirmed that it coincided with the spherical zinc oxide nanoparticles observed in the TEM photograph of FIG. 4 (a). TEM and SEM photographs of FIG. 4 confirm that the use of oleic acid is superior to that of PVP as a stabilizer for zinc oxide nanoparticles. This indicates that the carboxyl group of the oleic acid reacts with the charge on the surface of the zinc oxide and reacts to prevent aggregation of the zinc oxide nanoparticles. As a result, well-dispersed zinc oxide nanoparticles of 10 nm in size were obtained when oleic acid was used as a stabilizer. FIG. 4 (e) is a HR-TEM photograph of zinc oxide nanoparticles having an interplanar distance of about 0.25 nm, which is consistent with the (111) plane of hexagonal zinc oxide.
XRD pattern analysis of zinc oxide nanoparticles
Fig. 5 is a graph showing the relationship between Zn (IBC)2≪ / RTI > Zn (IBC)2The zinc oxide nanoparticles obtained by thermal decomposition showed the positions of the lattice in the unit crystals at the corresponding angles, and all peaks of the intrinsic θ range appeared and the peaks of pure hexagonal wurtzite zinc oxide nanoparticles (JCPDS No. 36-1451). Also, as shown in FIG. 5, it was confirmed that zinc oxide nanoparticles having excellent crystallinity were obtained, and zinc oxide peaks or impurities of other phases were not detected.
However, Zn (IBC)2Has been reported to act on moisture in the air to form a polynuclear zinc complex as follows: (Dell'Amico, D.B .; Calderazzo, F .; Labella, L .; Marchetti, F .; Mazzoncini, I.Inorg. Chim. Acta 2006,359, 3371).
4 Zn (O2CNHR)2 + H2O ↔ Zn4(μ4-O) (O2CNHR)6 + RHNCOO- +NH3R + CO2
As described above, the organic metal compound, zinc (II) isobutyl carbamate (Zn (IBC)2) Were used to prepare zinc oxide nanoparticles. Zn (IBC)2Isobutylamine and carbon dioxide (CO2),2Isobutylammonium isobutyl carbamate (IBA-IBC) was synthesized by the bubbling method. Zn (IBC)2Was synthesized by using IBA-IBC and zinc (Zn). The structure was analyzed and confirmed by FT-IR and NMR. At 120 < 0 > C, Zn (IBC)2The zinc oxide was prepared by the simple heat reduction method. Various parameters were controlled to control the size and shape of the zinc oxide particles. Spherical zinc oxide nanoparticles having a size of 20 nm or less were prepared using oleic acid as a stabilizer. The formation and properties of zinc oxide nanoparticles were analyzed and evaluated using TEM, UV-vis, XRD and the like.
<Summary of Production Examples 1 to 7 and Examples 1 to 13>
Production Example 1 produced a carbamate precursor of zinc oxide by pyrolysis and Production Example 2 produced zinc oxide carbamate precursor using 2-ethylhexylammonium 2-ethylhexylcarbamate (EHAEHC) and zinc chloride.
In Production Example 3, a bismuth (III) 2-ethylhexylcarbamate complex was produced because it was mainly yellow when bismuth ions were doped into various metal oxide matrices. At this time, the amount of EHAEBC was slightly overdose between 3.1-3.5 times because Bi was trivalent. Considering the solubility in water, the metal precursor of bismuth is Bi (NO3)3·
In Production Example 4, nickel (II) 2-ethylhexylcarbamate complex was produced because nickel ion acts as a green doping metal. The chemical structure of the nickel complex is known as nickel (II) di (2-ethylhexylcarbamate) (P. Biagini, G. Lugili, F. Calderazzo, DB Dell'Amico, A. Mergio, US patent 5,908, )).
In Production Example 5, an iron (III) 2-ethylhexylcarbamate complex was prepared because iron ions acted as a brown doping metal. The structure of the iron carbamate complex obtained by the two-component interfacial reaction is Fe2(NHCR)2(OOCNHR)4.
In Production Example 6, a cobalt (II) 2-ethylhexylcarbamate complex was prepared because cobalt ions acted as cyan and blue doping metals. The structure of the cobalt carbamate complex obtained by the two-component interfacial reaction is cobalt (II) di (2-ethylhexylcarbamate).
In Production Example 7, an aluminum (III) 2-ethylhexylcarbamate complex was prepared because aluminum ion acts as a cohost of the doping ion and the zinc oxide host. The structure of the aluminum carbamate complex obtained by the two-component interfacial reaction is aluminum (III) tri (2-ethylhexylcarbamate).
Nickel, iron, cobalt and an alumox complex for producing metal-doped ions and host ions in the above Production Examples 2 to 7 were prepared. Ceramic inks having various colors were prepared by mixing a doping metal carbamate and a host metal carbamate in an appropriate ratio in order to produce a ceramic ink.
In the ceramic ink expressing yellow in Example 1, the zinc (II) 2-ethylhexylcarbamate complex of Preparation Example 2 and the bismuth (III) 2-ethylhexylcarbamate complex of Preparation Example 3 were mixed at a ratio of 92:18 And dissolved in a hexane solvent. In consideration of the solubility and the boiling point of each metal complex, an alkane solvent such as heptane, octane, decane, and cyclohexane and an aromatic alkane such as benzene, toluene, xylene, and anisole are used in addition to hexane. In addition, chloroform, methylene chloride, ethyl acetate, and acetate monoalkyl ethers of ethylene glycol or diethylene glycol were also used.
The ceramic ink expressing the greenish-yellow color in Example 2 was obtained by mixing the zinc (II) 2-ethylhexylcarbamate complex of Preparation Example 2 and the nickel (II) 2-ethylhexylcarbamate complex of
Examples 3 and 10 produced a ceramic ink using a brown carbamate complex ceramic ink using iron ion and a green carbamate complex using cobalt ion. In Example 3-1, Example 4-1, Example 5-1 and Example 6, iron, cobalt, and aluminum ions were previously mixed with zinc ions in advance to easily form a carbamate complex.
In the cyan ceramic ink using the nickel ion and the zinc / silicon co-host of Example 5, the raw material of silicon is tetraethyl orthosilicate (Si (OC2H5)4Were used. The same effect was also obtained by using octamethylcyclotetrasiloxane. A blue ceramic ink using the cobalt ion of Example 16 and a zinc / aluminum cord host was prepared.
For the color development of the ceramic inks of Examples 1 to 6, solvents were removed from the six inks and firing was carried out. First, the mixed carbamate complex was firstly calcined at 300 ° C to remove residual organic matter, and then calcined at 1000 ° C for 1 hour. As shown in FIG. 7, the hexagonal Wurtzite zinc oxide matrix peaks of the respective inks were observed in the Ni / Zn / Si system and the Willemite phase simultaneously with the Wurtzite and Co / Zn / Respectively.
SEM photographs of the obtained ceramic pigments show the shape of the particles as shown in FIG. 8-13. The components of the pigments can be measured by EDS analysis. The ratio of the measured components was similar to that of the input metal ions.
Since the nanoparticles are formed at such a low temperature as described above, ceramic ink based on zinc oxide can be produced by firing a carbamate complex of similar dislocation metal, and they can be fired to produce ceramic pigments .
Similarly, the zinc (II) 2-ethylhexylcarbamate complex was prepared by synthesizing 2-ethylhexylammonium 2-ethylhexylcarbamate (EBAEHC). This was synthesized by the interfacial reaction in which zinc chloride was used as an aqueous solution and EBAEHC was dissolved in hexane, which is a nonpolar solvent which is not mixed with water.
Other carbamate complexes such as Bi, Ni, Fe, Co, Al and the like were prepared from each of the corresponding salts and EHAEBC and were mixed with zinc (II), bismuth (III), nickel (II) A 2-ethylhexylcarbamate complex of cobalt (II) and Al (III) was prepared. Six types of yellow, green, brown, green, cyan and blue ceramic inks were prepared by mixing these complexes. Ceramic pigments were also produced from these ceramic inks by firing.
The ceramic pigments according to the present invention are composed of metal oxides doped with transition metal ions or rare earth ions. The oxidation state and coordination number of these dopants determine the color properties of ceramic pigments. Color is also associated with partially filled d and f block elements. That is, the cobalt element exhibits various colors when doped into the oxide matrix of various metals. That is, Co2+Al2O3And Mg2B2O5 In the matrix, blue and rose colors appear, respectively, due to the four and six coordination numbers of cobalt.
However,2O4 It is blue when it is doped into the zinc spot of spinel. Therefore, zinc oxide can serve as a matrix as a single or binary metal oxide. To prepare a ceramic ink based on the zinc oxide, a zinc oxide preparation precursor is first prepared, and a ceramic ink thus prepared is simply manufactured and analyzed will be.
The scope of the present invention is not limited to the above-described embodiments, but may be embodied in various forms of embodiments within the scope of the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (24)
Preparing a metal carbamate precursor; And
Mixing the carbamate precursor and metal carbamate precursor of zinc oxide obtained above;
The method of producing a ceramic ink according to claim 1,
The carbamate precursor of zinc oxide is prepared by dissolving ammonium carbamate in a nonpolar solvent, dissolving the zinc salt in a polar solvent, and then mixing the ammonium carbamate and zinc salt dissolved in each of the solvents A method for producing a ceramic ink.
Wherein the carbamate precursor of zinc oxide is prepared by pyrolyzing zinc carbamate.
Wherein the carbamate precursor of zinc oxide is synthesized by phase transfer reaction of an ammonium carbamate dissolved in the non-polar solvent and a zinc salt dissolved in a polar solvent.
Wherein the zinc salt is at least one selected from the group consisting of zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc phosphate, zinc fluoride, zinc bromide and zinc iodide.
Wherein the carbamate precursor of zinc oxide is at least one selected from zinc (II) di (isobutyl carbamate), zinc (II) 2-ethylhexylcarbamate and zinc (II) di (2-ethylhexylcarbamate) ≪ / RTI >
Wherein the metal carbamate precursor is prepared by reacting a metal precursor with an ammonium carbamate.
Wherein the metal carbamate precursor is prepared by dissolving a metal precursor in a polar solvent, dissolving ammonium carbamate in a non-polar solvent, and reacting the metal precursor dissolved in each solvent with ammonium carbamate. ≪ / RTI >
The metal precursor may be at least one selected from the group consisting of copper oxide, zinc oxide, zinc chloride, vanadium oxide, nickel sulfide, palladium chloride, copper carbonate, iron chloride, gold chloride, nickel chloride, cobalt chloride, bismuth nitrate, vanadium acetylacetonate, There is provided a process for producing a polyimide precursor comprising the steps of reacting at least one selected from the group consisting of tin, manganous oxalate, gold acetate, palladium oxalate, copper 2-ethylhexanoate, iron stearate, nickel formate, ammonium molybdate, zinc citrate, bismuth acetate, cobalt cyanide, Characterized in that it is at least one selected from a salt or hydrate of metals consisting of titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, tin tetrafluoroborate, tantalum methoxide, dodecylmethacrylate gold and indium acetylacetonate Of the ceramic ink.
Wherein the ammonium carbamate is selected from the group consisting of ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t- , 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, di Butylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecyl carbamate, hexamethyleneimine ammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridinium ethyl hexyl carbamate, Triethylenediamine isopropyl carbamate, benzylammonium benzyl carbamate, and triethoxysilylpropylammonium triethoxysilylpropyl The process for producing a ceramic ink, characterized in that selected from the group consisting of carbamate at least one member.
The metal carbamate precursor may be selected from the group consisting of bismuth (III) 2-ethylhexylcarbamate, bismuth (III) tri (2-ethylhexylcarbamate), nickel (II) 2- ethylhexylcarbamate, nickel Ethylhexylcarbamate), iron (III) 2-ethylhexylcarbamate, cobalt (II) 2-ethylhexylcarbamate, cobalt A carbamate, and aluminum (III) tri (2-ethylhexylcarbamate).
The polar solvent is at least one selected from the group consisting of ethanol, methanol, acetone and water,
Wherein the nonpolar solvent is selected from the group consisting of alkane solvents selected from hexane, heptane, octane, decane and cyclohexane, aromatic alkanes selected from benzene, toluene, xylene and anisole, and organic solvents selected from the group consisting of chloroform, methylene chloride, ethyl acetate, ethylene glycol, and diethylene glycol Of at least one selected from the group consisting of acetone monoalkyl ethers of the formula (I).
Adding a stabilizer to the carbamate precursor of zinc oxide;
A method for producing zinc oxide nanoparticles for ceramic ink,
The carbamate precursor of zinc oxide is prepared by dissolving ammonium carbamate in a nonpolar solvent, dissolving the zinc salt in a polar solvent, and then mixing the ammonium carbamate and zinc salt dissolved in each of the solvents A method for producing zinc oxide nanoparticles.
Wherein the stabilizer is oleic acid. ≪ RTI ID = 0.0 > 11. < / RTI >
Preparing a metal carbamate precursor; And
Mixing the carbamate precursor and metal carbamate precursor of zinc oxide obtained above;
The method of manufacturing a ceramic pigment according to claim 1,
The carbamate precursor of zinc oxide is prepared by dissolving ammonium carbamate in a nonpolar solvent, dissolving the zinc salt in a polar solvent, and then mixing the ammonium carbamate and zinc salt dissolved in each of the solvents A method for producing ceramic pigments.
Removing the solvent of the mixed precursor solution; And
Calcining the solvent-removed precursor;
≪ / RTI > further comprising the steps of:
Wherein the calcination step comprises a first calcination step at 100 ° C to 500 ° C and a second calcination step at 500 ° C to 1500 ° C.
Wherein the metal carbamate precursor is prepared by dissolving a metal precursor in a polar solvent, dissolving ammonium carbamate in a non-polar solvent, and reacting the metal precursor dissolved in each solvent with ammonium carbamate. ≪ / RTI >
The metal precursor may be at least one selected from the group consisting of copper oxide, zinc oxide, zinc chloride, vanadium oxide, nickel sulfide, palladium chloride, copper carbonate, iron chloride, gold chloride, nickel chloride, cobalt chloride, bismuth nitrate, vanadium acetylacetonate, There is provided a process for producing a polyimide precursor comprising the steps of reacting at least one selected from the group consisting of tin, manganous oxalate, gold acetate, palladium oxalate, copper 2-ethylhexanoate, iron stearate, nickel formate, ammonium molybdate, zinc citrate, bismuth acetate, cobalt cyanide, Characterized in that it is at least one selected from a salt or hydrate of metals consisting of titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, tin tetrafluoroborate, tantalum methoxide, dodecylmethacrylate gold and indium acetylacetonate Gt; to < / RTI >
Wherein the ammonium carbamate is selected from the group consisting of ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t- , 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, di Butylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecyl carbamate, hexamethyleneimine ammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridinium ethyl hexyl carbamate, Triethylenediamine isopropyl carbamate, benzylammonium benzyl carbamate, and triethoxysilylpropylammonium triethoxysilylpropyl Selected from the group consisting of carbamate one kinds of method for producing a ceramic pigment, characterized in that at least.
Preparing a metal carbamate precursor; And
Mixing the carbamate precursor and metal carbamate precursor of zinc oxide obtained above;
The method of producing a ceramic ink according to claim 1,
Wherein the metal carbamate precursor is prepared by dissolving a metal precursor in a polar solvent, dissolving ammonium carbamate in a non-polar solvent, and reacting the metal precursor dissolved in each solvent with ammonium carbamate. ≪ / RTI >
The metal precursor may be at least one selected from the group consisting of copper oxide, zinc oxide, zinc chloride, vanadium oxide, nickel sulfide, palladium chloride, copper carbonate, iron chloride, gold chloride, nickel chloride, cobalt chloride, bismuth nitrate, vanadium acetylacetonate, There is provided a process for producing a polyimide precursor comprising the steps of reacting at least one selected from the group consisting of tin, manganous oxalate, gold acetate, palladium oxalate, copper 2-ethylhexanoate, iron stearate, nickel formate, ammonium molybdate, zinc citrate, bismuth acetate, cobalt cyanide, Characterized in that it is at least one selected from a salt or hydrate of metals consisting of titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, tin tetrafluoroborate, tantalum methoxide, dodecylmethacrylate gold and indium acetylacetonate Of the ceramic ink.
Wherein the ammonium carbamate is selected from the group consisting of ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t- , 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, di Butylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecyl carbamate, hexamethyleneimine ammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridinium ethyl hexyl carbamate, Triethylenediamine isopropyl carbamate, benzylammonium benzyl carbamate, and triethoxysilylpropylammonium triethoxysilylpropyl The process for producing a ceramic ink, characterized in that selected from the group consisting of carbamate at least one member.
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