KR20140128510A

KR20140128510A - Ceramic ink composite for inkjet printing

Info

Publication number: KR20140128510A
Application number: KR20130046452A
Authority: KR
Inventors: 한규성; 김진호; 황광택; 조우석; 이기찬
Original assignee: 한국세라믹기술원
Priority date: 2013-04-26
Filing date: 2013-04-26
Publication date: 2014-11-06
Also published as: WO2014175519A1

Abstract

The present invention relates to a ceramic ink composite for inkjet printing, capable of having excellent dispersion stability, color strength and colorfulness, being stable at high temperature, being printed without nozzle clogging during inkjet printing and being used when being printed on ceramic tiles and the like, and to a manufacturing method thereof.

Description

Technical Field [0001] The present invention relates to a ceramic ink composition for inkjet printing,

More particularly, the present invention relates to a ceramic ink composition and a method for producing the ceramic ink composition, and more particularly, to a ceramic ink composition having excellent dispersion stability, excellent color sharpness, excellent coloring power, stable at high temperature, Tile, and the like, and a method of manufacturing the same.

Ink-jet printing is a process technology in which fine ink droplets are ejected from a head to be patterned at a desired position. Inkjet printing is suitable for the implementation of complex shapes of small volumes in a non-contact manner. Such inkjet printing is a simple process, low waste of raw materials, less damage to the substrate, and an environmentally friendly process.

Pigments used in inkjet printing can be divided into size organic pigments and inorganic pigments.

Organic pigments have a disadvantage in that they are clear in color, have high coloring power and are easy to obtain a desired color tone, but are poor in heat resistance and light resistance, are mostly dissolved in organic solvents and unstable.

The inorganic pigment has a high light resistance and heat resistance and is stable to an organic solvent, but has a weak coloring power and a poor color sharpness.

In the case of using conventional inorganic pigments, technical problems such as nozzle clogging and dispersion instability occur when ink-jet printing is applied to a ceramic tile or the like.

In order to emphasize aesthetic effect when applied to a ceramic tile or the like, inks of a blue color system, a red color system, a yellow color system and a black color system which are four primary colors of digital color are required, Development of an ink composition having thermal stability and excellent color sharpness is required.

The object of the present invention is to provide an inkjet printing method which is excellent in dispersion stability, excellent in color sharpness, excellent in tinting strength, stable at a high temperature, capable of printing without clogging the nozzle during inkjet printing, And a method for producing the same.

The present invention relates to a method for producing a blue-colored ceramic pigment, which comprises at least one blue-based ceramic pigment selected from the group consisting of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≦ _x ≦ ₁ ) powder and Mg ₁ _- _x Ni _x Al ₂ O ₄ Wherein the ceramic pigment is dispersed in a dispersion and has a viscosity in the range of 10 to 30 cps, a surface tension in the range of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment in the range of 50 to 300 nm. .

The ceramic pigment is preferably contained in the ceramic ink composition for ink jet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion.

The dispersion may comprise at least one material selected from ethylene glycol and toluene.

The dispersion may further contain ethanol to improve the discharge characteristics and to control the viscosity and the surface tension, and the ethanol is preferably contained in the dispersion in an amount of 5 to 35% by volume.

In addition, the ceramic ink composition for inkjet printing may further comprise cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, dioctadecyldimethylammonium bromide and CH ₃ (CH ₂ ) ₁₅ N ( Br) (CH ₃ ) ₃ , and the cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dioctadecyldimethylammonium bromide, and CH ₃ (CH ₂ ) ₁₅ N (Br) CH ₃ ) ₃ is preferably contained in the ceramic ink composition for ink-jet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

The ceramic ink composition for inkjet printing may further comprise at least one material selected from sodium dodecylsulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na, and the sodium dodecyl sulfate and / CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na is preferably contained in the ceramic ink composition for inkjet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

The present invention also provides a coloring composition comprising a dispersion of a red ceramic pigment containing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder, having a viscosity of 10 to 30 cps and a surface tension of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment is in a range of 50 to 300 nm. The present invention also provides a ceramic ink composition for inkjet printing.

Ceramic ink composition for the ink-jet printing is a cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) (CH 3) 3 further comprises one or more materials that are selected from may be, the cetyl-trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) (CH 3) 3 1 or more materials that are selected from ceramic for the ink jet printing It is preferable that the ink composition is contained in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

The ceramic ink composition for inkjet printing may further comprise at least one material selected from sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na, wherein the sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na is preferably contained in the ceramic ink composition for ink-jet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

In addition, the present _{invention, Zr 1 - x Ce x SiO} 4 (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 - x Ta x SiO 4} (0.01 ? X? 0.5) powder is dispersed in a dispersion, the viscosity is in the range of 10 to 30 cps, the surface tension is in the range of 25 to 40 dyn / cm, and the average particle diameter of the ceramic pigment is Wherein the composition is in the range of 50 to 300 nm.

The present invention also provides a method for producing a black pigment, which comprises dispersing a black-based ceramic pigment containing a powder of Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) in a dispersion and having a viscosity of 10 to 30 cps, A tensile strength in the range of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment in the range of 50 to 300 nm.

The present invention also relates to a method for producing a powder of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 _? _X? ₁ ) and a powder of Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1? _X? 1) Preparing a ceramic pigment; pulverizing the ceramic pigment prepared to have an average particle size of 50 to 300 nm; and dispersing the pulverized resultant in a dispersion to have a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm The method comprising the steps of: preparing a ceramic ink composition for ink-jet printing;

A step of preparing the blue-based ceramic pigments, magnesium (Mg) oxide, Al ₂ O containing an oxide of CoO powder and the aluminum (Al) component including an oxide of MgO powder, a cobalt (Co) component comprising the component ₃ powder is prepared as a starting material at a molar ratio of 1-x: x: 1 (0.1? X? 1), or MgO powder as an oxide containing a magnesium (Mg) component, NiO as an oxide containing a nickel Preparing an Al ₂ O ₃ powder, which is an oxide including a powder and an aluminum (Al) component, as a starting material at a molar ratio of 1-x: x: 1 (0.1? X? 1) A step of subjecting the starting material to a solid phase reaction between the oxides while mechanically mixing and pulverizing the starting material, and calcining the pulverized product to obtain a powder of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≤ _x ≤ ₁ ) or Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1? X? 1) powders.

Cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) (CH 3) 3 can be further added one or more materials that are selected from time to disperse in the dispersion and, the cetyl-trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) (CH 3) 3 1 or more materials that are selected from a ceramic ink composition for the ink jet printing By weight based on 100 parts by weight of the dispersion.

In addition, one or more substances selected from sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na may be further added to the dispersion, and the sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na is added to the ceramic ink composition for inkjet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

The present invention also provides a method for producing a ceramic green pigment, comprising the steps of: preparing a red-based ceramic pigment containing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? X? 0.5) powder; pulverizing a ceramic pigment prepared to have an average particle size of 50 to 300 nm; Dispersing the resultant pulverized product in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm. to provide.

Wherein the step of preparing the red-based ceramic pigment comprises the steps of: CaO powder which is an oxide containing a Ca component; SnO powder which is an oxide containing a Sn component; Cr ₂ O ₃ which is an oxide containing a Cr component; Preparing an SiO ₂ powder as an oxide including a powder and a silicon (Si) component as a starting material so that Ca, Sn, Cr and Si have a molar ratio of 1: 1-x: x: 1 (0.01? X? 0.5) And a step of subjecting the starting material, the balls and the solvent to a solid-phase reaction between the oxides while mechanically mixing and pulverizing the starting material into a milling machine, and calcining the pulverized product to obtain CaSn _1-x Cr _x SiO ₄ (0.01? _X ? 0.5 ) Powder. &Lt; / RTI >

In addition, the present _{invention, Zr 1 - x Ce x SiO} 4 (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 - x Ta x SiO 4} (0.01 Lt; x < 0.5) powder, grinding the ceramic pigment prepared so as to have an average particle diameter of 50 to 300 nm, and dispersing the pulverized resultant in a dispersion to obtain a pigment having a viscosity of 10 to 30 cps and having a surface tension in the range of 25 to 40 dyn / cm. < RTI ID = 0.0 > A < / RTI >

The step of preparing the yellow-based ceramic pigment may include the steps of preparing a ZrO ₂ powder, an oxide containing a zirconium (Zr) component, a CeO ₂ powder, an oxide containing a cerium (Ce) the _second powder 1-x: x: 1 to prepare an oxide in a molar ratio of the starting material (0.01≤x≤0.5), or including an oxide of ZrO ₂ powder, praseodymium (Pr) component comprising a zirconium (Zr) component Pr ₂ O ₃ powder and SiO ₂ powder of silicon oxide containing a (Si) elements Zr, Pr and Si is 1-x: x: 1 ( 0.01≤x≤0.5) to achieve a molar ratio to prepare the starting material or of, Zr, Ta and Si are mixed with ZrO ₂ powder as an oxide containing a zirconium (Zr) component, Ta ₂ O ₅ powder as an oxide containing a tantalum (Ta) component and SiO ₂ powder as an oxide containing a silicon (Si) 1: x: x: 1 (0.01 < = x < = 0.5); and mixing the starting material, the balls and the solvent in a milling machine And a solid phase reaction between the oxides while mechanically mixing and pulverizing the starting material, and calcining the pulverized product to obtain a Zr _1-x Ce _x SiO ₄ (0.01? _X? 0.5) powder, Zr ₁ _- _x Pr _x SiO ₄ 0.01? _X? 0.5) powder or Zr ₁ _-x Ta _x SiO ₄ (0.01? _X? 0.5) powder.

The present invention also provides a method for producing a black pigment, comprising the steps of: preparing a black-based ceramic pigment comprising a powder of Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? X? 0.5); preparing a ceramic pigment having an average particle size of 50 to 300 nm And dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm. The ceramic ink composition for inkjet printing according to claim 1, A method for preparing a composition is provided.

The step of preparing the black-based ceramic pigment may include the steps of: preparing CoO powder as an oxide containing a cobalt (Co) component, Fe ₂ O ₃ powder as an oxide containing an iron (Fe) Cr ₂ O ₃ powder as a starting material at a molar ratio of 1: 1-x: x (0.01 ≦ x ≦ 0.5), placing the starting material, the balls and the solvent in a mill, mechanically mixing and pulverizing the starting material And a step of calcining the pulverized product to obtain Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder.

According to the present invention, it is possible to provide a ceramic ink for inkjet printing which is excellent in dispersion stability, excellent in color sharpness, excellent in coloring power, stable at high temperature, can be printed without clogging the nozzle during inkjet printing, A composition can be obtained.

The process for producing a ceramic ink composition for inkjet printing according to the present invention is simple in process and excellent in reproducibility.

1 is a graph showing an X-ray diffraction pattern according to a calcination temperature of a CoAl ₂ O ₄ powder synthesized after calcination according to Experimental Example 1 and an X-ray diffraction pattern before calcination.
FIG. 2A is a photograph showing the color development before calcination, and FIGS. 2B to 2F are photographs showing blue coloration of CoAl ₂ O ₄ powder synthesized after calcination for 3 hours according to Experimental Example 1 according to calcination temperature.
3 is a graph showing CIE La * b * according to the calcination temperature of CIE La * b * before calcination and CoAl ₂ O ₄ powder synthesized after calcination according to Experimental Example 1. FIG.
4A and 4B are scanning electron microscope (SEM) photographs showing the microstructure of CoAl ₂ O ₄ powder calcined at 1200 ° C. according to Experimental Example 1. FIG.
5A and 5B are graphs showing the results of EDS component analysis of CoAl ₂ O ₄ powder synthesized by calcination at 1200 ° C. according to Experimental Example 1. FIG.
6A to 6F are scanning electron microscope (SEM) photographs showing the microstructure of CoAl ₂ O ₄ powder according to the induction milling time.
7 is a graph showing the results of measurement of the particle size of CoAl ₂ O ₄ powder according to the induction milling time using a laser scattering particle size distribution analyzer.
8 is a graph showing the X-ray diffraction pattern after the induction milling before the induction milling and 3 hours.
Fig. 9 is a view showing the result of performing EDS component analysis on CoAl ₂ O ₄ powder after 3-hour induction milling.
10A and 10B are transmission electron microscope (TEM) photographs of CoAl ₂ O ₄ powder after 3-hour induction milling.
FIG. 11A is a photograph showing the color development for the CoAl ₂ O ₄ powder before the induction milling, and FIG. 11B is a photograph showing the color development for the CoAl ₂ O ₄ powder after the 3-hour induction milling.
12 is a graph showing CIE La * b * for CoAl ₂ O ₄ powder before and after 3-hour induction milling.
13A and 13B are transmission electron micrographs of a ceramic ink composition for inkjet printing formed by adding cetyltrimethylammonium bromide (CTAB).
14A and 14B are transmission electron micrographs of a ceramic ink composition for inkjet printing formed by adding sodium dodecyl sulfate (SDS).
15 is a photograph showing the dispersion stability depending on the surfactant and the dispersion liquid.
16A to 16D are photographs showing the tinting strength according to the content of the CoAl ₂ O ₄ powder.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

The ceramic ink composition for inkjet printing according to the first embodiment of the present invention is characterized in that a powder of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 _? _X? ₁ ) and a powder of Mg ₁ _- _x Ni _x Al ₂ O ₄ x? 1) powders are dispersed in a dispersion, the viscosity is in the range of 10 to 30 cps, the surface tension is in the range of 25 to 40 dyn / cm, the average particle diameter of the ceramic pigment is 50 To 300 nm.

The ceramic ink composition for ink-jet printing comprises cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, dioctadecyldimethylammonium bromide and CH ₃ (CH ₂ ) ₁₅ N (Br) (CH ₃ ) ₃ , and the cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dioctadecyldimethylammonium bromide, and CH ₃ (CH ₂ ) ₁₅ N (Br) (CH ₃ ) ₃ is preferably contained in the ceramic ink composition for inkjet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

The ceramic ink composition for inkjet printing according to the second preferred embodiment of the present invention is characterized in that a red ceramic pigment containing CaSn ₁ _- _x Cr _x SiO ₄ (0.01 _? _X ? 0.5) powder is dispersed in a dispersion and has a viscosity of 10 To 30 cps, a surface tension in the range of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment in the range of 50 to 300 nm.

The ceramic ink composition for inkjet printing according to the third embodiment of the present invention comprises Zr ₁ _- _x Ce _x SiO ₄ (0.01 ≦ _x ≦ 0.5) powder, Zr ₁ _- _x Pr _x SiO ₄ (0.01 ≦ _x ≦ 0.5) And at least one yellow-based ceramic pigment selected from Zr ₁ _-x Ta _x SiO ₄ (0.01? _X? 0.5) powder is dispersed in the dispersion, the viscosity is in the range of 10 to 30 cps, the surface tension is 25 to 40 dyn / cm, and the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm.

The ceramic ink composition for inkjet printing according to the fourth preferred embodiment of the present invention is characterized in that a black ceramic pigment containing Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder is dispersed in a dispersion , A viscosity in the range of 10 to 30 cps, a surface tension in the range of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment in the range of 50 to 300 nm.

A method for producing a ceramic ink composition for inkjet printing according to a first embodiment of the present invention comprises the steps of mixing Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 _? _X? ₁ ) powder and Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1 &le; x &le; 1) powder; grinding the ceramic pigment prepared so as to have an average particle diameter of 50 to 300 nm; dispersing the pulverized product in a dispersion to obtain a dispersion liquid having a viscosity of 10 To 30 cps and a surface tension in the range of 25 to 40 dyn / cm.

A method for preparing a ceramic ink composition for inkjet printing according to a second embodiment of the present invention comprises the steps of preparing a red ceramic pigment containing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) Milling a ceramic pigment prepared to have an average particle size of ~ 300 nm and dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm do.

The preferred method for manufacturing the ceramic ink composition for ink-jet printing according to the third embodiment of the present _{invention, Zr 1 - x Ce x SiO} 4 (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x 0.5) powder and a Zr ₁ _- _x Ta _x SiO ₄ (0.01 _? _X? 0.5) powder, and grinding the ceramic pigment prepared to have an average particle size of 50 to 300 nm And dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm.

A method for producing a ceramic ink composition for ink jet printing according to a fourth embodiment of the present invention comprises preparing a black ceramic pigment containing a powder of Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) Milling a ceramic pigment prepared to have an average particle size of 50 to 300 nm and dispersing the pulverized resultant in a dispersion to form a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm .

In addition, one or more substances selected from the group consisting of sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na may be further added to the dispersion, and the sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na is added to the ceramic ink composition for inkjet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

Hereinafter, embodiments according to the present invention will be specifically shown, and the present invention is not limited to the following embodiments.

&Lt; Example 1 >

CoAl ₂ O ₄ has an AB ₂ O ₄ structure and is thermally and chemically stable as a spinel structure. Since CoAl ₂ O ₄ stably produces blue color at high temperature, it can be used as a ceramic pigment of high-hardness blue system. Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 _{? X? 1} ) or Mg _1-x Ni _x Al ₂ O ₄ (0.1? _X? ₁ ) has a spinel structure, So that it can be used as a blue pigment ceramic pigment.

First, a blue-based ceramic pigment, Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 _? _X? ₁ ) powder or Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1? _X? ₁ ) The synthesis method will be described.

The preparation of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≤ _x ≤ ₁ ) powder or Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1 ≤ _x _≤ ₁ ) powder using the solid phase method is carried out by using an oxide powder (For example, 1000 to 1450 ° C) in order to obtain a spinel crystal structure after a solid state reaction is performed by mixing the materials at a target ratio by ball mill, attrition mill, It undergoes the process of calcination.

Hereinafter, a method of synthesizing a blue-based ceramic pigment, Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1? _X? ₁ ) powder or Mg ₁ _-x Ni _x Al ₂ O ₄ (0.1? _X? ₁ ) This will be described in detail.

Prepare the starting material.

MgO powder can be used as an oxide powder containing a magnesium (Mg) component as a starting material for synthesizing Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≦ _x ≦ 1) powder, and a cobalt (Co) CoO powder may be used as the oxide powder to be included, and Al ₂ O ₃ powder may be used as the oxide powder containing aluminum (Al) component. An oxide powder containing a magnesium (Mg) component, an oxide powder containing a cobalt (Co) component and an oxide powder containing an aluminum (Al) component has a molar ratio of 1-x: x: 1 Prepare to do. At this time, when the content of the oxide powder including the magnesium (Mg) component is 0 (when x is 1 in the molar ratio of 1-x: x: 1), CoAl ₂ O ₄ powder is synthesized.

MgO powder may be used as a starting material for synthesizing the Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1 ≦ _x ≦ 1) powders as an oxide powder containing a magnesium (Mg) component, and a nickel (Ni) NiO powder may be used as the oxide powder to be included, and Al ₂ O ₃ powder may be used as the oxide powder containing aluminum (Al) component. An oxide powder containing a magnesium (Mg) component, an oxide powder containing a nickel (Ni) component and an oxide powder containing an aluminum (Al) component have a molar ratio of 1-x: x: 1 Prepare to do. At this time, when the content of the oxide powder containing magnesium (Mg) component is 0 (when x is 1 at a molar ratio of 1-x: x: 1), NiAl ₂ O ₄ powder is synthesized.

The prepared starting materials are mechanically mixed and milled to give a solid phase reaction between the oxides.

For this purpose, the starting material, balls and solvent are charged into a milling machine such as a ball mill or an induction mill. The starting materials are milled while mixing uniformly using a milling machine. At this time, the solid phase reaction occurs between the oxide powders by the energy due to the collision between the balls and the starting materials, balls and balls, balls and milling machines. During the milling process, the oxide powder as a starting material reacts with each other due to the collision energy. As the solvent, water, alcohol such as ethanol and the like can be used.

The ball used in the milling machine may be a ball made of ceramics such as alumina or zirconia, and the balls may be all the same size or may be used together with balls having two or more sizes.

The size of the balls, the weight ratio of the balls and the oxide powder, the milling time, the rotation speed of the milling machine, and the like are adjusted to be the size of the target oxide powder particles. For example, in consideration of the size of the oxide powder particles, the size of the balls is preferably set in the range of about 1 to 50 mm, and the rotational speed of the milling machine is preferably set in the range of about 300 to 1200 rpm. The milling is preferably performed for 1 to 48 hours in consideration of the size of the target particle, the degree of the solid-phase reaction, and the like. If the milling time is less than 1 hour, sufficient solid reaction may not occur. Even if the milling time exceeds 48 hours, the amount of decrease in the particle size of the powder is insignificantly limited to reduce the particle size and is not economical. The ball and the starting material to be fed into the mill are preferably in a weight ratio of about 20 to 150: 1. If the content of the balls relative to the starting material is too small, sufficient pulverization may not be performed, which may limit the agglomeration of the particles and the size of the particles, and is not effective when the content of the balls relative to the starting material is too large.

When milling is carried out by a milling machine, the size of the particles decreases, the direct contact area of the reactive oxide powders increases, and a solid phase reaction occurs. By milling, oxide powders as a starting material are pulverized into fine particles, have a uniform particle size distribution, and are mixed uniformly. In the milling machine, mechanical polishing by balls and chemical reaction by solid phase reaction occur simultaneously And mechanical chemical treatment is performed.

The resultant mixture is dried using a milling machine, charged into a furnace such as an electric furnace, and calcined. The calcination step is preferably carried out at a calcination temperature of about 1000 to 1450 DEG C for about 1 to 24 hours. The calcination temperature is preferably raised at a heating rate of 1 to 50 占 폚 / min. If the heating rate is too slow, the time is long and productivity is deteriorated. If the heating rate is too fast, thermal stress is applied due to a rapid temperature rise It is preferable to raise the temperature at the temperature raising rate in the above range. The calcination is preferably carried out in an oxidizing atmosphere (for example, oxygen (O ₂ ) or air atmosphere). After the calcination process is performed, the furnace temperature is lowered to obtain a calcined powder of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≤ _x ≤ ₁ ) or Mg _{1 -} _x Ni _x Al ₂ O ₄ (0.1 ≤ _x ≤ 1) Unload the powder. The furnace cooling may be effected by shutting down the furnace power source to cool it in a natural state, or optionally by setting a temperature decreasing rate (for example, 10 DEG C / min).

At least one blue-based ceramic selected from Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 _? _X? ₁ ) powder and Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1? _X? 1) A blue-based ceramic ink composition is prepared using a pigment.

In order to uniformly crush the blue-based ceramic pigment, it is charged into a milling machine such as a ball mill or an induction mill. The ball and the solvent are put into a mill and the blue ceramic pigment is mechanically crushed. It is preferable to crush the ceramic pigment so that the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm. As the solvent, water, alcohol such as ethanol and the like can be used.

The size of the balls, the weight ratio of the balls and the ceramic pigment, the milling time, and the rotational speed of the milling machine are adjusted so as to be crushed to the size of the desired ceramic pigment particle. For example, in consideration of the size of the ceramic pigment particles, the size of the balls is preferably set in the range of about 1 to 50 mm, and the rotation speed of the milling machine is preferably set in the range of about 100 to 1200 rpm. The milling is preferably performed for 1 to 48 hours in consideration of the size of the target particle and the like. The weight of the balls and the ceramic pigment to be fed into the milling machine is preferably about 20 to 150: 1 by weight. If the content of the balls to the ceramic pigment is too small, sufficient pulverization can not be carried out, so there may be a limit to miniaturize the agglomeration of the particles or the size of the particles, and it is not effective when the content of the balls to the ceramic pigment is too large.

When crushed by a milling machine, as the particle size becomes smaller, the ceramic pigment is pulverized into fine particles and has a uniform particle size distribution.

The pulverized ceramic pigment is dried. The drying is preferably performed at a temperature of about 30 to 150 ° C.

The dried ceramic pigment is added to and dispersed in the dispersion to prepare a blue-based ceramic ink composition. It is preferable that the ceramic pigment is dispersed in the dispersion so that the viscosity of the ceramic ink composition is in the range of 10 to 30 cps and the surface tension is in the range of 25 to 40 dyn / cm. The ceramic pigment is preferably contained in the ceramic ink composition for ink jet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion. The dispersion may be ethylene glycol, toluene or a mixture thereof.

The dispersion may further contain ethanol as a non-thickening agent for improving the discharging property of the ceramic ink composition and for controlling the viscosity and the surface tension. The ethanol is preferably contained in the dispersion in an amount of 5 to 35% by volume.

When the ceramic pigment is dispersed in the dispersion, a surfactant may be further added. The surfactant is preferably added to the ceramic ink composition for ink-jet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion. The surfactant may be selected from the group consisting of cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTAC), dioctadecyldimethylammonium bromide (DODAB) and CH ₃ (CH ₂ ) ₁₅ N Br) (CH ₃ ) ₃ , or at least one cationic surfactant selected from sodium dodecylsulfate (SDS) and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na, It is preferable to use a surfactant.

&Lt; Example 2 >

The CaSn ₁ _- _x Cr _x SiO ₄ (0.01 _≤ _x _≤ 0.5) powder is thermally and chemically stable. _{CaSn 1 -x Cr x SiO 4 (} 0.01≤x≤0.5) powder is stable at high temperatures, so that the color of the red color (red) series can be also used as a solidified ceramic pigment of the red system.

First, a method of synthesizing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder as a red ceramic pigment is described by using a solid phase method.

The preparation of CaSn ₁ _- _x Cr _x SiO ₄ (0.01 _≤ _x _≤ 0.5) powders by the solid phase method is carried out by mixing ball mills, attrition mills, etc., Followed by calcination at a relatively low temperature (e.g., 1000 to 1450 ° C) to obtain a spinel crystal structure.

Hereinafter, a method of synthesizing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder as a red ceramic pigment will be described in more detail.

Prepare the starting material.

CaO powder may be used as a starting material for synthesizing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder as an oxide powder containing calcium (Ca) SnO 2 powder may be used as the oxide powder, Cr ₂ O ₃ powder may be used as the oxide powder including the chromium (Cr) component, and SiO ₂ powder may be used as the oxide powder containing the silicon (Si) component. An oxide powder containing a calcium (Ca) component, an oxide powder containing a tin (Sn) component, an oxide powder containing a chromium (Cr) component and an oxide powder containing a silicon (Si) Si is prepared so as to have a molar ratio of 1: 1-x: x: 1 (0.01? X? 0.5).

The resultant mixture is dried using a milling machine, charged into a furnace such as an electric furnace, and calcined. The calcination step is preferably carried out at a calcination temperature of about 1000 to 1450 DEG C for about 1 to 24 hours. The calcination temperature is preferably raised at a heating rate of 1 to 50 占 폚 / min. If the heating rate is too slow, the time is long and productivity is deteriorated. If the heating rate is too fast, thermal stress is applied due to a rapid temperature rise It is preferable to raise the temperature at the temperature raising rate in the above range. The calcination is preferably carried out in an oxidizing atmosphere (for example, oxygen (O ₂ ) or air atmosphere). After the calcination process is performed, the furnace temperature is lowered to unload the calcined powder of CaSn ₁ _- _x Cr _x SiO ₄ (0.01 _≤ _x _≤ 0.5). The furnace cooling may be effected by shutting down the furnace power source to cool it in a natural state, or optionally by setting a temperature decreasing rate (for example, 10 DEG C / min).

A red ceramic ink composition is prepared using a red ceramic pigment containing CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder synthesized as described above.

In order to uniformly crush the red ceramic pigment, it is charged into a milling machine such as a ball mill or an induction mill. The ball and the solvent are put into a mill and the red ceramic pigment is mechanically crushed. It is preferable to crush the ceramic pigment so that the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm. As the solvent, water, alcohol such as ethanol and the like can be used.

The dried ceramic pigment is added to the dispersion and dispersed to prepare a red-based ceramic ink composition. It is preferable that the ceramic pigment is dispersed in the dispersion so that the viscosity of the ceramic ink composition is in the range of 10 to 30 cps and the surface tension is in the range of 25 to 40 dyn / cm. The ceramic pigment is preferably contained in the ceramic ink composition for ink jet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion. The dispersion may be ethylene glycol, toluene or a mixture thereof.

&Lt; Example 3 >

_{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 -x Ta x SiO 4 (} 0.01≤x≤0.5) powder Are thermally and chemically stable. _{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 - x Ta x SiO 4} (0.01≤x≤0.5) powder Can be used as a ceramic pigment of high yellowing degree because it develops a yellow color stably at high temperature.

First, by using a conventional method and a yellow pigment-based ceramic _{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder or Zr ₁ _- _x A method of synthesizing a Ta _x SiO ₄ (0.01? _X? 0.5) powder will be described.

Using the conventional method and _{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder or _{Zr 1 - x Ta x SiO 4} (0.01≤x ≤0.5) Powders were prepared by mixing the oxide powders as starting materials at desired ratios and then performing a ball mill, attrition mill, etc. to obtain a solid phase reaction and then obtaining a spinel crystal structure For example, at a relatively low temperature (e.g., 1000 to 1450 ° C).

In the following, a yellow pigment-based ceramic of _{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 -x Pr x SiO 4} (0.01≤x≤0.5) powder or Zr ₁ _- _x Ta _x SiO ₄ (0.01 < = x < = 0.5) powder will be described in more detail.

Prepare the starting material.

ZrO ₂ powder can be used as an oxide powder containing a zirconium (Zr) component as a starting material for synthesizing a Zr ₁ _- _x Ce _x SiO ₄ (0.01 ≦ _x ≦ 0.5) powder, and a cerium (Ce) CeO ₂ powder may be used as the oxide powder, and SiO ₂ powder may be used as the oxide powder containing the silicon (Si) component. An oxide powder containing a zirconium (Zr) component, an oxide powder containing a cerium (Ce) component and an oxide powder containing a silicon (Si) component has a molar ratio of 1-x: x: 1 As a starting material.

ZrO ₂ powder can be used as an oxide powder containing a zirconium (Zr) component as a starting material for synthesizing a Zr ₁ _- _x Pr _x SiO ₄ (0.01 ≦ _x ≦ 0.5) powder, and a praseodymium (Pr) Pr ₂ O ₃ powder may be used as the oxide powder, and SiO ₂ powder may be used as the oxide powder containing the silicon (Si) component. The oxide powder containing a zirconium (Zr) component, the oxide powder containing a praseodymium (Pr) component, and the oxide powder containing a silicon (Si) Lt; / = 0.5) as a starting material.

_{Zr 1 - x Ta x SiO 4} (0.01≤x≤0.5) from a raw material for synthesizing the powder used may be a ZrO ₂ powder with an oxide powder containing zirconium (Zr) ingredient, including tantalum (Ta) component A Ta ₂ O ₅ powder may be used as the oxide powder, and SiO ₂ powder may be used as the oxide powder containing a silicon (Si) component. An oxide powder containing a zirconium (Zr) component, an oxide powder containing a tantalum (Ta) component and an oxide powder containing a silicon (Si) component is a mixture of Zr, Ta and Si in the range of 1-x: x: 1 Lt; / = 0.5) as a starting material.

The resultant mixture is dried using a milling machine, charged into a furnace such as an electric furnace, and calcined. The calcination step is preferably carried out at a calcination temperature of about 1000 to 1450 DEG C for about 1 to 24 hours. The calcination temperature is preferably raised at a heating rate of 1 to 50 占 폚 / min. If the heating rate is too slow, the time is long and productivity is deteriorated. If the heating rate is too fast, thermal stress is applied due to a rapid temperature rise It is preferable to raise the temperature at the temperature raising rate in the above range. The calcination is preferably carried out in an oxidizing atmosphere (for example, oxygen (O ₂ ) or air atmosphere). After the calcination process, the furnace temperature is lowered to obtain a calcined powder of Zr ₁ _- _x Ce _x SiO ₄ (0.01 ≦ _x ≦ 0.5) powder, Zr ₁ _-x Pr _x SiO ₄ (0.01 ≦ _x ≦ 0.5) powder or Zr ₁ _- _x Ta _x SiO ₄ (0.01? _X? 0.5) powder is unloaded. The furnace cooling may be effected by shutting down the furnace power source to cool it in a natural state, or optionally by setting a temperature decreasing rate (for example, 10 DEG C / min).

The Zr ₁ synthesized as described above _{- x Ce x SiO 4 (0.01≤x≤0.5} ) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 - x Ta x SiO 4} (0.01≤ x &le; 0.5) powders, the yellow based ceramic ink composition is prepared.

In order to uniformly crush the yellow-based ceramic pigment, it is charged into a milling machine such as a ball mill or an induction mill. The balls and solvent are put in a mill and the yellow based ceramic pigment is mechanically crushed. It is preferable to crush the ceramic pigment so that the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm. As the solvent, water, alcohol such as ethanol and the like can be used.

The dried ceramic pigment is added to the dispersion and dispersed to prepare a yellow-based ceramic ink composition. It is preferable that the ceramic pigment is dispersed in the dispersion so that the viscosity of the ceramic ink composition is in the range of 10 to 30 cps and the surface tension is in the range of 25 to 40 dyn / cm. The ceramic pigment is preferably contained in the ceramic ink composition for ink jet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion. The dispersion may be ethylene glycol, toluene or a mixture thereof.

Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder is thermally and chemically stable. _{Co (Fe 1 -x Cr x)} 2 O 4 (0.01≤x≤0.5) powder is stable at high temperatures, so that the color of the black color (black) sequence it is possible to also use a ceramic pigment solidification of a black grid.

First, a method of synthesizing a black color ceramic pigment Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder is described by using a solid phase method.

The preparation of Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01 _≤ _x _≤ 0.5) powders by the solid phase method is carried out by mixing the oxide powders to be used as the starting materials at desired ratios and using ball mills, attrition mills mill) and the like to cause a solid-phase reaction, and then undergoes a calcination process at a relatively low temperature (for example, 1000 to 1450 ° C) to obtain a spinel crystal structure.

Hereinafter, a method of synthesizing a black color ceramic pigment Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder will be described in more detail.

Prepare the starting material.

As a starting material for synthesizing Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder, CoO powder may be used as an oxide powder containing cobalt (Co) The Fe ₂ O ₃ powder may be used as the oxide powder containing the Cr component, and the Cr ₂ O ₃ powder may be used as the oxide powder containing the Cr component. An oxide powder containing a cobalt (Co) component, an oxide powder containing an iron (Fe) component and an oxide powder containing a chromium (Cr) component has a molar ratio of 1: 1-x: x Prepare as starting material.

The resultant mixture is dried using a milling machine, charged into a furnace such as an electric furnace, and calcined. The calcination step is preferably carried out at a calcination temperature of about 1000 to 1450 DEG C for about 1 to 24 hours. The calcination temperature is preferably raised at a heating rate of 1 to 50 占 폚 / min. If the heating rate is too slow, the time is long and productivity is deteriorated. If the heating rate is too fast, thermal stress is applied due to a rapid temperature rise It is preferable to raise the temperature at the temperature raising rate in the above range. The calcination is preferably carried out in an oxidizing atmosphere (for example, oxygen (O ₂ ) or air atmosphere). After the calcination process is performed, the furnace temperature is lowered to unload the resultant calcined powder of Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5). The furnace cooling may be effected by shutting down the furnace power source to cool it in a natural state, or optionally by setting a temperature decreasing rate (for example, 10 DEG C / min).

A black color ceramic ink composition is prepared by using a black color ceramic pigment containing Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder synthesized as described above.

In order to uniformly crush the black ceramic pigment, it is charged into a milling machine such as a ball mill or an induction mill. The balls and solvent are placed in a mill and the black ceramic pigment is mechanically crushed. It is preferable to crush the ceramic pigment so that the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm. As the solvent, water, alcohol such as ethanol and the like can be used.

The dried ceramic pigment is added to the dispersion and dispersed to prepare a black-based ceramic ink composition. It is preferable that the ceramic pigment is dispersed in the dispersion so that the viscosity of the ceramic ink composition is in the range of 10 to 30 cps and the surface tension is in the range of 25 to 40 dyn / cm. The ceramic pigment is preferably contained in the ceramic ink composition for ink jet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion. The dispersion may be ethylene glycol, toluene or a mixture thereof.

Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited by the following experimental examples.

CoAl ₂ O ₄ powder, a blue ceramic pigment, was synthesized by solid state method.

In the preparation of CoAl ₂ O ₄ powder using the solid phase method, the oxide powders as the starting materials were mixed according to the target ratios and ball mills, attrition mills, and the like were performed, Lt; RTI ID = 0.0 > 1400 C. < / RTI >

Hereinafter, a method of synthesizing a CoAl ₂ O ₄ powder that is a blue-based ceramic pigment will be described in more detail.

The starting material was prepared.

As a starting material for the synthesis of CoAl ₂ O ₄ powder, CoO powder was used as an oxide powder containing cobalt (Co) component, and Al ₂ O ₃ powder was used as an oxide powder containing aluminum (Al) component. An oxide powder containing a cobalt (Co) component and an oxide powder containing an aluminum (Al) component were prepared so as to have a molar ratio of 1: 1. The oxide powder containing cobalt (Co) was sieved with a sieve of 325 mesh, and the oxide powder containing aluminum (Al) component had an average particle size of about 300 탆.

The prepared starting materials were mechanically mixed and milled to give a solid phase reaction between the oxides.

For this purpose, starting materials, balls and solvent were charged into a ball mill. The starting materials were milled while mixing uniformly using a milling machine. At this time, the solid phase reaction occurs between the oxide powders by the energy due to the collision between the balls and the starting materials, balls and balls, balls and milling machines. During the milling process, the oxide powder as a starting material reacts with each other due to the collision energy. Ethanol was used as the solvent. The ball used in the milling machine was a ball made of zirconia (ZrO ₂ ). The balls were about 1 mm in size, and the milling machine was set at a rotational speed of about 800 rpm and milling was performed for 3 hours. The ball and the starting material introduced into the mill were about 100: 1 by weight.

The resultant mixture was dried using a milling machine, charged into an electric furnace, and calcined. The calcination was carried out at a calcination temperature of 1000 to 1400 캜 for 3 hours. The calcination temperature was raised at a heating rate of 5 DEG C / min. The calcination was carried out in an air atmosphere. After the calcination process, the furnace temperature was lowered to unload the resultant CoAl ₂ O ₄ powder. The cooling of the electric furnace was made to cool down in a natural state by shutting off the power supply.

FIG. 1 is a graph showing an X-ray diffraction (XRD) pattern according to a calcination temperature of a CoAl ₂ O ₄ powder synthesized after calcination according to Experimental Example 1 and an X-ray diffraction pattern before calcination.

Referring to FIG. 1, CoO and Al ₂ O ₃ crystal phases appear before calcination. After calcination at 1000 ° C, 1100 ° C, 1200 ° C, 1300 ° C and 1400 ° C, only the CoAl ₂ O ₄ crystal phase was observed.

FIG. 2A is a photograph showing color development before calcination, and FIGS. 2B to 2F are photographs showing blue coloration depending on calcination temperature of CoAl ₂ O ₄ powder synthesized after calcination according to Experimental Example 1. FIG. Fig. 2B shows a case of calcination at 1000 DEG C, Fig. 2C shows a case of calcination at 1100 DEG C, Fig. 2D shows a case of calcination at 1200 DEG C, Fig. 2E shows a case of calcination at 1300 DEG C, It is a case of calcination.

Referring to Figs. 2A to 2F, blue is not developed before calcination. When calcined at 1000 ° C, 1100 ° C, 1200 ° C, 1300 ° C and 1400 ° C, blue color is developed. It showed dark blue color at 1000 ℃, which is low calcination temperature, and high clarity of blue color when calcined at 1200 ℃ or more.

FIG. 3 is a graph showing CIE La * b * according to the calcination temperature of CIE La * b * before calcination and CoAl ₂ O ₄ powder synthesized after calcination according to Experimental Example 1, and Table 1 shows CIE La * b * . In FIG. 3, 'before' represents calcination.

L a * b * Calcination 42.38 1.08 1.09 1000 ℃ 34.27 -9.45 -19.64 1100 ℃ 40.60 -15.88 -29.34 1200 ℃ 42.98 -13.45 -37.82 1300 ℃ 35.79 -8.84 -37.03 1400 ° C 38.55 -8.10 -40.15

Referring to Table 1 and FIG. 3, when the calcination temperature is low, the brightness of blue is low at 1000 ° C. and when the calcination is at 1200 ° C. or more, the brightness of blue is high.

4A and 4B are scanning electron microscope (SEM) photographs showing the microstructure of CoAl ₂ O ₄ powder calcined at 1200 ° C. according to Experimental Example 1. FIG.

4A and 4B, CoAl ₂ O ₄ powder calcined and synthesized according to Experimental Example 1 was found to be aggregated.

5A and 5B show the results of EDS component analysis of the CoAl ₂ O ₄ powder synthesized by calcination at 1200 ° C. according to Experimental Example 1, and the results of the component analysis for FIG. 5A are shown in Table 2 below The results of component analysis for 5b are shown in Table 3 below.

ingredient Weigth% Atomic% O K 39.97 61.10 Al K 28.47 25.81 Co K 31.56 13.10 Totals 100.00

ingredient Weigth% Atomic% O K 39.72 61.02 Al K 28.04 25.54 Co K 32.24 13.45 Totals 100.00

5A, 5B, 2 and 3, it was confirmed that the CoAl ₂ O ₄ powder synthesized according to Experimental Example 1 contained cobalt (Co), aluminum (Al), and oxygen (O) .

The blue color ceramic ink composition was prepared using the blue color ceramic pigment of CoAl ₂ O ₄ powder calcined at 1200 ° C as described above.

The blue color ceramic pigment CoAl ₂ O ₄ powder was charged into an induction mill to uniformly crush the powder. The ball and the solvent were put into a mill and the CoAl ₂ O ₄ powder was mechanically pulverized. Ethanol was used as the solvent.

The ball used in the milling machine was a ball made of zirconia (ZrO ₂ ). The ball was about 1 mm in diameter, and the milling machine was rotated at a speed of about 800 rpm. Milling was performed for 1 to 5 hours. The ball and CoAl ₂ O ₄ powder added to the mill were about 100: 1 by weight.

The ground CoAl ₂ O ₄ powder was dried. The drying was carried out at a temperature of about 80 캜 for about 1 hour.

6A to 6F are SEM photographs showing the microstructure of the CoAl ₂ O ₄ powder according to the induction milling time, and FIG. 7 is a photograph of the particle size of the CoAl ₂ O ₄ powder according to the induction milling time And a laser scattering particle size distribution analyzer according to the present invention. FIG. 6A shows the microstructure of the CoAl ₂ O ₄ powder before performing the induction milling, FIG. 6B shows the case where the induction milling was performed for 1 hour, FIG. 6C shows the case where the induction milling was performed for 2 hours FIG. 6D shows the case where the attraction milling is performed for 3 hours, FIG. 6E shows the case where the attraction milling is performed for 4 hours, and FIG. 6F shows the case where the attraction milling is performed for 5 hours.

Referring to FIGS. 6A to 7, the particle size of the CoAl ₂ O ₄ powder was found to decrease with increase in the induction milling time. After 3 hours, the decreasing rate of particle size was small.

8 is a graph showing the X-ray diffraction pattern after the induction milling before the induction milling and 3 hours.

Referring to Fig. 8, only the CoAl ₂ O ₄ crystal phase was observed before and after the induction milling.

FIG. 9 shows the results of EDS component analysis for CoAl ₂ O ₄ powder after 3-hour induction milling, and the results of the component analysis are shown in Table 4 below.

ingredient Weigth% Atomic% O K 34.47 57.97 Al K 25.62 25.55 Co K 29.17 13.32 Zr L 10.74 3.17 Totals 100.00

9 and Table 4, it was judged that a small amount of Zr impurity was contained in the ceramic pigment from the zirconia (ZrO ₂ ) ball used for the attrition milling, and the major component content was not greatly changed.

10A and 10B are transmission electron microscope (TEM) photographs of CoAl ₂ O ₄ powder after 3-hour induction milling.

Referring to FIGS. 10A and 10B, CoAl ₂ O ₄ powder after 3-hour induction milling was observed to have a particle size of about 200 nm.

FIG. 11A is a photograph showing the color development for the CoAl ₂ O ₄ powder before the attrition milling, FIG. 11B is a photograph showing the color development for the CoAl ₂ O ₄ powder after the 3-hour attrition milling, FIG. 5 is a graph showing CIE La * b * for CoAl ₂ O ₄ powder before and after 3-hour induction milling, and Table 5 shows CIE La * b *.

L a * b * Before Attrition Milling 42.98 -13.45 -37.82 After attrition milling 38.97 -8.69 -32.37

Referring to Figs. 11A to 12, after the attrition milling, the color was slightly darkened, but there was no significant difference in the blue coloration.

The dried CoAl ₂ O ₄ powder and cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS) were added to the dispersion and dispersed to prepare a blue-based ceramic ink composition.

The CoAl ₂ O ₄ powder was contained in the ceramic ink composition for ink-jet printing in an amount of 15 wt%, and the dispersion contained 84.95 wt% in the ink-jet printing ceramic ink composition. The cetyltrimethylammonium bromide (CTAB) Silica sulfate (SDS) was contained in the ceramic ink composition for ink jet printing in an amount of 0.05 wt%. As the dispersion, a mixed solution of ethylene glycol and ethanol was used.

13A and 13B are transmission electron micrographs of a ceramic ink composition for inkjet printing formed by addition of cetyltrimethylammonium bromide (CTAB), and FIGS. 14A and 14B are photographs of inkjet prints formed by adding sodium dodecylsulfate (SDS) 2 is a transmission electron micrograph of a ceramic ink composition for printing.

13A to 14B, it was observed that the dispersion was good when cetyltrimethylammonium bromide (CTAB) was added. When sodium dodecyl sulfate (SDS) was added, cetyltrimethylammonium bromide (CTAB) was added Showed a slightly cohesive appearance.

Table 6 below shows the viscosities of the dispersions with the contents of ethylene glycol (EG) and ethanol (volume%).

100% by volume of ethylene glycol 90% by volume of ethylene glycol and 10% by volume of ethanol 80% by volume of ethylene glycol and 20% 70% by volume of ethylene glycol and 30% by volume of ethanol, 60% by volume of ethylene glycol and 40% by volume of ethanol, 50% by volume of ethylene glycol and 50% by volume of ethanol, 18.67 cps 14.78 cps 11.52 cps 8.85 cps 6.86 cps 5.25 cps

Table 7 below shows the viscosity and surface tension of the ceramic ink composition according to the content of the dispersion.

Configuration 15% by weight of CoAl ₂ O ₄ powder, 0.05% by weight of CTAB, 84.95% by weight of dispersion (a mixture of 80% by volume of ethylene glycol and 20% by volume of ethanol) 15% by weight of CoAl ₂ O ₄ powder, 0.05% by weight of CTAB, 84.95% by weight of dispersion (a mixture of 70% by volume of ethylene glycol and 30% by volume of ethanol) Viscosity 19.20 cps 15.61 cps Surface tension 33.06 dyn / cm 31.18 dyn / cm

CoAl ₂ O ₄ powder dried according to Experimental Example 1 was added to and dispersed in the dispersion to prepare a blue-based ceramic ink composition. At this time, cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS) was optionally added or not added.

The CoAl ₂ O ₄ powder was contained in the ceramic ink composition for ink-jet printing in an amount of 15 wt%, and the dispersion contained 84.95 wt% in the ink-jet printing ceramic ink composition. The cetyltrimethylammonium bromide (CTAB) Silica sulfate (SDS) was contained in the ceramic ink composition for ink jet printing in an amount of 0.05 wt%. When no surfactant was added, the CoAl ₂ O ₄ powder was contained in the ceramic ink composition for ink-jet printing in an amount of 15 wt%, and the dispersion was contained in the ceramic ink composition for inkjet printing in an amount of 85 wt%. Water or a mixed solution of ethylene glycol and ethanol was used as the dispersion.

15 is a photograph showing the dispersion stability depending on the surfactant and the dispersion liquid. In FIG. 15, 'Di' represents the case where water is used as a dispersion without adding a surfactant, 'EG' represents a case where ethylene glycol and ethanol are used as a dispersion without adding a surfactant, 'EG + CTA' represents cetyltrimethyl 'EG + SDS' is the case where sodium dodecyl sulfate (SDS) and a mixture of ethylene glycol and ethanol are used as the dispersion.

Referring to Fig. 15, dispersion stability was found to be high when an organic (ethylene glycol) was used as a dispersion rather than a water (water). The addition of ethylene glycol and cetyltrimethylammonium bromide (CTAB) showed no significant difference in dispersion stability with ethylene glycol (EG). The addition of ethylene glycol (EG) and sodium dodecyl sulfate (SDS) .

CoAl ₂ O ₄ powder and cetyltrimethylammonium bromide (CTAB) dried according to Experimental Example 1 were added to and dispersed in the dispersion to prepare a blue-based ceramic ink composition.

The CoAl ₂ O ₄ powder is contained in the ceramic ink composition for inkjet printing in an amount of 10 to 30 wt% and the dispersion contains 69.95 to 89.95 wt% of the ceramic ink composition for inkjet printing. The cetyltrimethylammonium bromide (CTAB ) Was contained in the ceramic ink composition for ink-jet printing in an amount of 0.05% by weight. The dispersion used was a mixed solution of ethylene glycol and ethanol (80% by volume of ethylene glycol and 20% by volume of ethanol).

16A to 16D are photographs showing the tinting strength according to the content of the CoAl ₂ O ₄ powder. 16A shows a case where CoAl ₂ O ₄ powder is contained at 10 wt% in a ceramic ink composition for ink-jet printing, FIG. 16B shows a case where CoAl ₂ O ₄ powder is contained at 15 wt% in a ceramic ink composition for inkjet printing, is the case and if the CoAl ₂ O ₄ powder contained 20% by weight of the ceramic ink composition for ink-jet printing, Fig. 16d is a CoAl ₂ O ₄ powder contained 20% by weight of the ceramic ink composition for ink-jet printing.

16A to 16D, when the CoAl ₂ O ₄ powder was contained in the ceramic ink composition for ink-jet printing at 15 wt%, the coloring power was the most excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

Claims

At least one blue-based ceramic pigment selected from the group consisting of Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≦ _x ≦ ₁ ) powder and Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1 ≦ _x ≦ 1) A viscosity in the range of 10 to 30 cps, a surface tension in the range of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment in the range of 50 to 300 nm.

Based ceramic pigment comprising CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder dispersed in a dispersion, having a viscosity in a range of 10 to 30 cps, a surface tension in a range of 25 to 40 dyn / cm, Wherein the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm.

_{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 -x Ta x SiO 4 (} 0.01≤x≤0.5) powder , A viscosity in the range of 10 to 30 cps, a surface tension in the range of 25 to 40 dyn / cm, and an average particle diameter of the ceramic pigment in the range of 50 to 300 nm Wherein the ceramic ink composition is ink-jet printing.

_{Co (Fe 1 - x Cr x} ) 2 O 4 (0.01≤x≤0.5) and a black pigment-based ceramic containing powder is dispersed to the dispersion, and a viscosity of cps range 10~30, 25~40 so that the surface tension dyn / cm, and the average particle diameter of the ceramic pigment is in the range of 50 to 300 nm.

The ceramic ink for ink-jet printing according to any one of claims 1 to 4, wherein the ceramic pigment is contained in the ceramic ink composition for inkjet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion. Composition.

5. The ceramic ink composition for inkjet printing according to any one of claims 1 to 4, wherein the dispersion comprises at least one substance selected from the group consisting of ethylene glycol and toluene.

The ceramic ink composition for inkjet printing according to claim 6, wherein the dispersion further comprises ethanol for improving the discharge characteristics and for controlling the viscosity and the surface tension, and the ethanol is contained in the dispersion in an amount of 5 to 35% .

Claim 1 to claim 4 according to any one of wherein the ceramic ink for ink-jet printing compositions of the term is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br ) (CH ₃₎ further comprising one or more materials that are selected from _3,
The cetyl-trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) (CH 3) 3 1 or more materials that are selected from the above in a ceramic ink composition for the ink jet printing 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion.

The ceramic ink composition for ink jet printing according to any one of claims 1 to 4, further comprising at least one substance selected from sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na ,
The at least one material selected from sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na is contained in the ceramic ink composition for ink jet printing in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion By weight based on the weight of the ink composition.

Preparing at least one blue-based ceramic pigment selected from a Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1 ≤ _x ≤ ₁ ) powder and a Mg ₁ _- _x Ni _x Al ₂ O ₄ (0.1 ≤ _x ≤ 1) ;
Pulverizing a ceramic pigment prepared to have an average particle size of 50 to 300 nm; And
Dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm.

Preparing a red-based ceramic pigment comprising CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder;
Pulverizing a ceramic pigment prepared to have an average particle size of 50 to 300 nm; And
Dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm.

_{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 - x Pr x SiO} 4 (0.01≤x≤0.5) powder and a _{Zr 1 -x Ta x SiO 4 (} 0.01≤x≤0.5) powder The method comprising the steps of: preparing at least one yellow-based ceramic pigment selected from among yellow,
Pulverizing a ceramic pigment prepared to have an average particle size of 50 to 300 nm; And
Dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm.

Preparing a black based ceramic pigment comprising a Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5) powder;
Pulverizing a ceramic pigment prepared to have an average particle size of 50 to 300 nm; And
Dispersing the pulverized resultant in a dispersion to obtain a ceramic ink composition having a viscosity in the range of 10 to 30 cps and a surface tension in the range of 25 to 40 dyn / cm.

11. The method of claim 10, wherein preparing the blue-based ceramic pigment comprises:
Al ₂ O ₃ powder, which is an oxide including MgO powder, CoO powder and Co (Al), which is an oxide including a magnesium (Mg) component, an oxide including a cobalt (Co) 0.1? X? 1), or an oxide containing Mg (Mg), an oxide containing Ni (Ni), and an oxide containing Al Preparing a starting Al ₂ O ₃ powder as a starting material at a molar ratio of 1-x: x: 1 (0.1? X? 1);
Placing the starting material, the balls and the solvent in a milling machine and mechanically mixing and pulverizing the starting material to cause a solid phase reaction between the oxides; And
And calcining the pulverized product to obtain a Mg ₁ _- _x Co _x Al ₂ O ₄ (0.1? _X? ₁ ) powder or Mg _{1 -} _x Ni _x Al ₂ O ₄ (0.1? _X? ₁ ) powder Wherein the ink composition comprises at least one of the following compounds.

12. The method of claim 11, wherein preparing the red-based ceramic pigment comprises:
(CaO) powder which is an oxide containing a calcium (Ca) component, a SnO powder which is an oxide including a tin (Sn) component, Cr ₂ O ₃ powder which is an oxide including a chromium (Cr) Preparing SiO ₂ powder as a starting material so that Ca, Sn, Cr and Si have a molar ratio of 1: 1-x: x: 1 (0.01? X? 0.5);
Placing the starting material, the balls and the solvent in a milling machine and mechanically mixing and pulverizing the starting material to cause a solid phase reaction between the oxides; And
And calcining the pulverized product to obtain a CaSn ₁ _- _x Cr _x SiO ₄ (0.01? _X? 0.5) powder. The method for producing a ceramic ink composition for inkjet printing according to claim 1,

13. The method of claim 12, wherein preparing the yellow based ceramic pigment comprises:
ZrO ₂ powder as an oxide containing a zirconium (Zr) component, CeO ₂ powder as an oxide containing a cerium (Ce) component, SiO ₂ powder as an oxide containing a silicon (Si) prepared in a molar ratio of 0.01≤x≤0.5) as starting materials, or zirconium (Zr) component oxide is ZrO ₂ powder, praseodymium (Pr ₂ O ₃ in the oxide powder and silicon (Si) component comprising Pr) component comprising the oxide is SiO ₂ powder, Zr, Pr, and the Si 1-x, including: x: an oxide including one prepared as a starting material, or to achieve a mole ratio of (0.01≤x≤0.5) zirconium (Zr) component ZrO ₂ : Ta ₂ O ₅ powder, which is an oxide containing tantalum (Ta), and SiO ₂ powder, which is an oxide including a silicon (Si) Lt; / = 0.5) as a starting material;
Placing the starting material, the balls and the solvent in a milling machine and mechanically mixing and pulverizing the starting material to cause a solid phase reaction between the oxides; And
Calcining the pulverized resultant _{Zr 1 - x Ce x SiO 4} (0.01≤x≤0.5) _{powder, Zr 1 -x Pr x SiO 4} (0.01≤x≤0.5) powder or _{Zr 1 - x Ta x SiO 4} (0.01 &Lt; / = x < / = 0.5). &Lt; / RTI >

14. The method of claim 13, wherein preparing the black based ceramic pigment comprises:
Cobalt (Co) component oxide, CoO powder, iron (Fe) component oxide is Fe ₂ O ₃ powder, chromium (Cr) component oxide is Cr ₂ O ₃ powder 1 comprising a containing containing: 1-x : preparing a starting material at a molar ratio of x (0.01? x? 0.5);
Placing the starting material, the balls and the solvent in a milling machine and mechanically mixing and pulverizing the starting material to cause a solid phase reaction between the oxides; And
And calcining the pulverized product to obtain a powder of Co (Fe ₁ _- _x Cr _x ) ₂ O ₄ (0.01? _X ? 0.5).

The ceramic ink for inkjet printing according to any one of claims 10 to 13, wherein the ceramic pigment is contained in the ceramic ink composition for inkjet printing in an amount of 10 to 43 parts by weight based on 100 parts by weight of the dispersion. &Lt; / RTI >

14. The method of any one of claims 10 to 13, wherein the dispersion comprises at least one material selected from the group consisting of ethylene glycol and toluene.

The ceramic ink composition for inkjet printing according to claim 19, wherein the dispersion further comprises ethanol for improving the discharge characteristics and for controlling the viscosity and the surface tension, and the ethanol is contained in the dispersion in an amount of 5 to 35% &Lt; / RTI >

A method according to any one of claims 10 to 13, when dispersed in the dispersion cetyltrimethylammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) ( CH ₃ ) ₃ is further added,
The cetyl-trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, and _{CH 3 (CH 2) 15 N} (Br) (CH 3) one or more kinds selected from the _third material is the dispersion 100 parts by weight of the ceramic ink composition And 0.001 to 3 parts by weight based on 100 parts by weight of the total weight of the ceramic ink composition.

11. The method of claim 10 according to any one of claims 13, further addition of sodium dodecyl sulfate and _{CH 3 (CH 2) 10 CH} 2 1 or more materials selected from the group consisting of OSO ₃ Na when dispersed in the dispersion,
Wherein at least one substance selected from the group consisting of sodium dodecyl sulfate and CH ₃ (CH ₂ ) ₁₀ CH ₂ OSO ₃ Na is contained in the ceramic ink composition in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the dispersion. &Lt; / RTI >