CN106634216B - High-weather-resistance water-based ceramic pattern-penetrating ink with stable storage and preparation method thereof - Google Patents
High-weather-resistance water-based ceramic pattern-penetrating ink with stable storage and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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Abstract
The invention belongs to the field of fine chemicals for ceramic industry, and particularly relates to high-weather-resistance water-based ceramic bleeding ink with stable storage and a preparation method thereof. The bleeding ink comprises the following components in parts by mass: 100 parts of aqueous color development ink, 0.5-10 parts of aqueous organic acid zinc/quaternary ammonium salt ionic liquid and 0.5-10 parts of water-soluble micromolecule nitrogen-containing polydentate coordination compound. The pattern penetrating ink is subjected to penetrating drying and high-temperature firing at 800-1250 ℃ for 5-1 h on the surface of a ceramic blank glaze, so that a pattern with high weather resistance is presented. And the pattern-permeating ink has lasting storage stability in high and low temperature environments and good vertical permeability on ceramic blank glaze.
Description
Technical Field
The invention belongs to the field of fine chemicals for ceramic industry, and particularly relates to high-weather-resistance water-based ceramic bleeding ink with stable storage and a preparation method thereof.
Background
Oxide pigment chromonic inks in the micron or submicron particle size have found wide application in the ceramic industry. However, the particle type oxide chromophoric pigment substance is not only very easy to settle and separate in a dispersion medium, but also very easy to block a printing nozzle during printing, thereby seriously influencing the production and use efficiency and the use effect and limiting the further popularization and use of the substance. The soluble dye-based color-developing ink has many outstanding advantages, such as easy configuration of color-developing ink, stable color-developing ink configuration, difficult blockage of printing nozzles, easy penetration of printing media, wide selection range, low cost and the like. However, the organic dye molecules have poor ageing resistance such as sun resistance and ozone resistance, and the dye is colored, oxidized and carbonized at high temperature, so that the organic dye molecules cannot be used in occasions with high temperature and weather resistance requirements.
The ceramic digital ink-jet printing technology is a ceramic surface decoration technology, the bleeding color-developing ink is a novel low-viscosity bleeding ink, several units have been developing ceramic oil-based bleeding inks at home and abroad, but for water-based ceramic bleeding inks, particularly high-weather-resistance water-based ceramic bleeding inks with stable storage, no relevant literature reports on the preparation method and the use of the water-based ceramic bleeding inks are found.
Disclosure of Invention
The invention aims to provide a high-weather-resistance water-based ceramic bleeding ink which is stable in storage.
The invention also aims to provide a preparation method of the high-weather-resistance water-based ceramic bleeding ink with stable storage.
The purpose of the invention is realized by the following technical scheme:
the storage-stable high-weather-resistance water-based ceramic bleeding ink comprises the following components in parts by mass:
100 parts by mass of aqueous color developing ink
0.5-10 parts by mass of aqueous organic acid zinc/quaternary ammonium salt type ionic liquid
0.5-10 parts by mass of a water-soluble micromolecule nitrogen-containing polydentate coordination compound.
Preferably, the aqueous color-developing ink is a solution having a pH of 4 to 7 prepared by dissolving and dispersing a water-soluble color-developing metal compound organic acid salt in an aqueous solvent at 60 ℃ or lower.
More preferably, the water-soluble chromophoric metal compound organic acid salt is an organic acid salt containing a plurality of coordination atoms, and comprises at least one of tartrate, citrate, amino acid salt, ethylene diamine tetraacetic acid sodium salt, diethylenetriamine pentaacetic acid sodium salt and N-hydroxyethyl ethylenediamine triacetic acid salt.
More preferably, the aqueous solvent includes at least one of water, formic acid, acetic acid, acrylic acid, methacrylic acid, ethanol, isopropanol, diacetone alcohol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, glycerol, N-dimethylformamide, and N, N-dimethylacetamide; the content of water in the aqueous solvent is not less than 70% of the total mass of the aqueous solvent.
Preferably, the aqueous zinc organic acid salt/quaternary ammonium salt type ionic liquid contains both aqueous zinc organic acid salt and quaternary ammonium salt type ionic liquid.
More preferably, the aqueous organic acid zinc is at least one of zinc acetate, zinc amino acid, zinc picolinate, zinc tartrate and sodium zinc ethylenediaminetetraacetate.
More preferably, the cation of the quaternary ammonium salt type ionic liquid is imidazolium and its derivative [ R1R2im]+Or [ R ]1R2R3im]+The anion is Cl－、Br－、BF4－、PF6 －、CF3COO－、C3F7COO－Or CF3SO3 －。
Preferably, the water-soluble micromolecule nitrogen-containing polydentate coordination compound is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, N-aminoethyl piperazine, hydroxyethyl ethylenediamine, hydroxyethyl diethylenetriamine, monoethanolamine, diethanolamine, triethanolamine, N-dimethyl monoethanolamine, carbamyl hydrazine, oxalyl hydrazine, disodium ethylene diamine tetraacetate, amino acid and N-hydroxyethyl ethylenediamine triacetic acid.
A preparation method of high-weather-resistance water-based ceramic bleeding ink with stable storage comprises the following steps: uniformly mixing 100 parts by mass of aqueous coloring ink, 0.5-10 parts by mass of aqueous organic acid zinc/quaternary ammonium salt ionic liquid and 0.5-10 parts by mass of water-soluble micromolecule nitrogenous polydentate coordination compound at room temperature (15-30 ℃) to obtain the storage-stable and non-deterioration aqueous ceramic ink for penetrating patterns. The pattern penetrating ink is subjected to penetrating drying and high-temperature firing at 800-1250 ℃ for 5-1 h on the surface of a ceramic blank glaze, so that a pattern with high weather resistance is presented.
The actual use condition of the ink-jet printing at the temperature of 30-50 ℃ is considered in the bleeding ink, the stability in storage in low-temperature environment in winter and the contact with air is also considered, and particularly the low-temperature storage stability of the dissolving type water-based ink is not negligible. Aqueous materials often decay by the action of airborne microorganisms during exposure to air. The quaternary ammonium salt is an effective antibacterial agent and has a certain inhibiting effect on microorganisms. The quaternary ammonium type ionic liquid is a green solvent with the advantages of high stability, low volatility, acid-base adjustability, designability and the like, and meanwhile, the ionic liquid has strong self-assembly capacity, is favorable for stabilizing the aqueous color developing ink and improving the vertical permeability of the ink to a ceramic substrate, so that the color developing ink can fully permeate into the substrate. The water-soluble chromophoric metal compound organic acid salt has better stability under the complexing stabilization action of the water-soluble micromolecule nitrogen-containing polydentate coordination compound, and can keep long-term stability under the condition of keeping the solvent non-volatile under the environment of high temperature of 50 ℃ and low temperature of 5 ℃. The water-based organic acid zinc has a synergistic effect on the antibacterial activity of the quaternary ammonium ionic liquid, forms a colored hybrid structure inorganic metal oxide together with organic acid salt in the luminous ink at a high temperature, and simultaneously the colored metal oxide is wrapped by the cured glaze in a molten state at a high temperature, so that the surface layer structure is compact, and the weather resistance is very excellent.
Compared with the prior art, the invention has the following outstanding characteristics and advantages:
(1) the pattern penetrating ink has lasting storage stability in high and low temperature environments, and has good vertical permeability on ceramic blank glaze;
(2) the color of the infiltrated ink after high-temperature sintering has excellent weather resistance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The process is conventional unless otherwise specified, and the starting materials are commercially available from published sources. The following examples are all in parts by mass.
Example 1
Mixing, dissolving and dispersing 10 parts of N-hydroxyethyl ethylenediamine ferric triacetate in a medium of 65 parts of water, 5 parts of acetic acid, 15 parts of ethylene glycol and 5 parts of ethylene glycol monomethyl ether at the room temperature of 25 ℃ to prepare 100 parts of color development ink, and measuring the pH value to be 4; then adding 6 parts of ethylene diamine tetraacetic acid zinc sodium, 4 parts of 1-butyl-3-methyl chloro imidazole ionic liquid (abbreviated as [ Bmim ] Cl) and 0.5 part of N-hydroxyethyl ethylenediamine triacetic acid at room temperature, and uniformly stirring to obtain the high-weather-resistance water-based ceramic bleeding ink with stable storage. Then, according to the same method, the storage stability of the ink which is half volume of air and half volume of ink and is stored in a sealed manner under the high-temperature and low-temperature (50 ℃ and 5 ℃) environment is respectively tested, and whether the ink has the changes of precipitation, suspension, phase separation and the like is observed for more than 3 months and 6 months continuously. And dropping the ink on the ceramic body glaze at room temperature, carrying out infiltration drying, then carrying out high-temperature sintering at 800 ℃ for 5 hours, cooling, taking out, and observing whether the color part of the ink fired color part has changes of color change, light loss, whitening, bubbling, softening, shedding, rusting and the like respectively according to the acid resistance (GB/T1733-1993: 5% sulfuric acid concentration is soaked, alkali resistance (GB/T1733-1993: 5% NaOH concentration is soaked for 168 hours), salt water resistance (GB 1763-79: 3% sodium chloride solution is soaked for 168 hours) and ultraviolet aging resistance (GB/T23987-2009: 1000 hours) of the coating.
Example 2
25 parts of disodium manganese ethylenediamine tetraacetate and 10 parts of iron N-hydroxyethyl ethylenediamine triacetate are mixed, dissolved and dispersed in 65 parts of water at the temperature of 60 ℃ to prepare 100 parts of color development ink, and the pH value is measured to be 7 after the color development ink is cooled to room temperature; then, 0.5 part of zinc picolinate and 1-butyl-3-methyl hexafluoro-phosphoimidazole ionic liquid (abbreviated as [ Bmim ] are added at room temperature]PF6)0.5 part of monoethanolamine, 0.2 part of diethanolamine and 5 parts of water-based ceramic ink with high weather resistance and stable storage is obtained after even stirring. Then, according to the same method, the storage stability of the ink which is half volume of air and half volume of ink and is stored in a sealed manner under the high and low temperature (50 ℃ and 5 ℃) environment is respectively tested, and whether the ink is separated out or suspended is observed for more than 3 months and 6 months continuouslyPhase separation, etc. And dropping the ink on the ceramic body glaze at room temperature, carrying out infiltration drying, then carrying out high-temperature sintering at 1250 ℃ for 1 hour, cooling, taking out, and observing whether the color part of the ink fired is changed by color change, light loss, whitening, bubbling, softening, shedding, rusting and the like after the color part of the ink fired is respectively soaked for 168 hours according to the acid resistance (GB/T1733 + 1993: 5% sulfuric acid concentration, alkali resistance (GB/T1733 + 1993: 5% NaOH concentration), salt water resistance (GB 1763-79: 3% sodium chloride solution for 168 hours) and ultraviolet aging resistance (GB/T23987 + 2009:1000 hours) of the coating.
Example 3
Mixing, dissolving and dispersing 10 parts of ferric ammonium citrate and 5 parts of ethylene diamine tetraacetic acid ferric sodium at 40 ℃ in a medium of 70 parts of water, 10 parts of propylene glycol and 5 parts of diacetone alcohol, and cooling to room temperature to measure the pH value to be 6; then, 0.5 part of zinc glycinate and 1-butyl-3-methyl boron tetrafluoride imidazole (abbreviated as [ Bmim ] are added at room temperature]BF4)1 part and 0.5 part of disodium ethylene diamine tetraacetate are uniformly stirred to obtain the high-weather-resistance water-based ceramic ink for infiltrating patterns, which is stable in storage. Then, according to the same method, the storage stability of the ink which is half volume of air and half volume of ink and is stored in a sealed manner under the high-temperature and low-temperature (50 ℃ and 5 ℃) environment is respectively tested, and whether the ink has the changes of precipitation, suspension, phase separation and the like is observed for more than 3 months and 6 months continuously. And dropping the ink on the ceramic body glaze at room temperature, carrying out infiltration drying, sintering at the high temperature of 1200 ℃ for 2 hours, cooling, taking out, and observing whether the color part of the ink fired is changed by color change, light loss, whitening, bubbling, softening, shedding, rusting and the like after the color part of the ink fired is respectively soaked for 168 hours according to the acid resistance (GB/T1733 + 1993: sulfuric acid concentration is 5 percent, alkali resistance (GB/T1733 + 1993: NaOH concentration is 5 percent), salt water resistance (GB 1763-79: 3 percent sodium chloride solution is soaked for 168 hours) and ultraviolet aging resistance (GB/T23987 + 2009:1000 hours) of the coating.
Example 4
Mixing, dissolving and dispersing 8 parts of sodium ferric ethylene diamine tetraacetate and 8 parts of ferrous tartrate in a medium of 80 parts of water and 4 parts of ethylene glycol at 30 ℃, cooling to room temperatureMeasuring the pH value to be 6; then, 0.3 part of zinc tartrate and 1-butyl-3-methyltrifluoroacetic acid imidazole (abbreviated as [ Bmim ] are added at room temperature]CF3COO)0.3 part, N-dimethyl monoethanolamine 0.5 part and carbamyl hydrazine 0.1 part, and stirring uniformly to obtain the high weather resistance water-based ceramic ink for bleeding. Then, according to the same method, the storage stability of the ink which is half volume of air and half volume of ink and is stored in a sealed manner under the high-temperature and low-temperature (50 ℃ and 5 ℃) environment is respectively tested, and whether the ink has the changes of precipitation, suspension, phase separation and the like is observed for more than 3 months and 6 months continuously. And dropping the ink on the ceramic body glaze at room temperature, carrying out infiltration drying, then carrying out high-temperature sintering at 1000 ℃ for 2 hours, cooling, taking out, and observing whether the color of the ink-fired color part changes such as color change, light loss, whitening, bubbling, softening, falling, rusting and the like after respectively carrying out soaking according to the acid resistance of the coating (GB/T1733 + 1993: 5% sulfuric acid concentration, soaking for 168 hours in alkali resistance (GB/T1733 + 1993: 5% NaOH concentration), salt water resistance (GB 1763-79: 3% sodium chloride solution for 168 hours) and ultraviolet aging resistance (GB/T23987 + 2009:1000 hours).
Example 5
Mixing 5 parts of diethylenetriamine pentaacetic acid iron sodium salt and 15 parts of ferric ammonium citrate at 50 ℃, dissolving and dispersing in a medium of 70 parts of water, 5 parts of glycerol and 5 parts of N, N-dimethylformamide, cooling to room temperature, and measuring the pH value to be 6; then adding 0.3 part of zinc acetate, [ Bmim ] Cl 1 part and 3 parts of serine at room temperature, and uniformly stirring to obtain the high-weather-resistance water-based ceramic ink for penetrating patterns, which is stable in storage. Then, according to the same method, the storage stability of the ink which is half volume of air and half volume of ink and is stored in a sealed manner under the high-temperature and low-temperature (50 ℃ and 5 ℃) environment is respectively tested, and whether the ink has the changes of precipitation, suspension, phase separation and the like is observed for more than 3 months and 6 months continuously. And dropping the ink on the ceramic body glaze at room temperature, carrying out infiltration drying, then carrying out high-temperature sintering at 900 ℃ for 4 hours, cooling, taking out, and observing whether the color of the ink-fired color part changes such as color change, light loss, whitening, bubbling, softening, falling off, rusting and the like after respectively carrying out soaking on the ink-fired color part according to the acid resistance (GB/T1733 + 1993: 5% sulfuric acid concentration, soaking for 168 hours in 5% NaOH concentration), salt water resistance (GB 1763-79: 3% sodium chloride solution soaking for 168 hours) and ultraviolet aging resistance (GB/T23987 + 2009:1000 hours) of the coating.
Example 6
Mixing, dissolving and dispersing 5 parts of copper glycinate and 10 parts of sodium copper ethylene diamine tetraacetate in a medium of 65 parts of water, 18 parts of N, N-dimethylacetamide and 2 parts of dipropylene glycol at 40 ℃, and cooling to room temperature to measure the pH value to be 6; then adding 0.5 part of zinc glycinate, 0.5 part of 1-butyl-3-methyl bromo imidazole (abbreviated as [ Bmim ] Br), 0.4 part of hydroxyethyl ethylenediamine and 0.1 part of ethylenediamine at room temperature, and uniformly stirring to obtain the high-weather-resistance water-based ceramic bleeding ink with stable storage. Then, according to the same method, the storage stability of the ink which is half volume of air and half volume of ink and is stored in a sealed manner under the high-temperature and low-temperature (50 ℃ and 5 ℃) environment is respectively tested, and whether the ink has the changes of precipitation, suspension, phase separation and the like is observed for more than 3 months and 6 months continuously. And dropping the ink on the ceramic body glaze at room temperature, carrying out infiltration drying, then carrying out high-temperature sintering at 1000 ℃ for 3 hours, cooling, taking out, and observing whether the color of the ink-fired color part changes such as color change, light loss, whitening, bubbling, softening, falling, rusting and the like after respectively carrying out soaking according to the acid resistance of the coating (GB/T1733 + 1993: 5% sulfuric acid concentration, soaking for 168 hours in alkali resistance (GB/T1733 + 1993: 5% NaOH concentration), salt water resistance (GB 1763-79: 3% sodium chloride solution for 168 hours) and ultraviolet aging resistance (GB/T23987 + 2009:1000 hours).
Table 1: ink storage stability and high-temperature sintering color and color weatherability
As can be seen from Table 1, the water-based ceramic flower-penetrating ink prepared by the invention has long storage stability in air-containing and high-temperature and low-temperature environments. The color of the pattern-penetrating ink after being subjected to penetration drying and sintering at 800-1250 ℃ for 5-1 hours on the surface of the ceramic blank glaze shows excellent corrosion resistance (acid resistance, alkali resistance and salt water resistance) and ultraviolet aging resistance, and has excellent weather resistance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. The storage-stable high-weather-resistance water-based ceramic bleeding ink is characterized by comprising the following components in parts by mass:
100 parts by mass of aqueous color developing ink
0.5-10 parts by mass of aqueous organic acid zinc/quaternary ammonium salt type ionic liquid
0.5-10 parts by mass of a water-soluble micromolecule nitrogen-containing polydentate coordination compound;
the aqueous color development ink is a solution with a pH value of 4-7, which is prepared by dissolving and dispersing a water-soluble color development metal compound organic acid salt in an aqueous solvent at room temperature or below 60 ℃;
the water-soluble color development metal compound organic acid salt is organic acid salt containing a plurality of coordination atoms, and comprises at least one of tartrate, citrate, amino acid salt, ethylene diamine tetraacetic acid sodium salt, diethylenetriamine pentaacetic acid sodium salt and N-hydroxyethyl ethylenediamine triacetate;
the aqueous solvent comprises at least one of water, formic acid, acetic acid, acrylic acid, methacrylic acid, ethanol, isopropanol, diacetone alcohol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, glycerol, N-dimethylformamide and N, N-dimethylacetamide; the content of water in the aqueous solvent containing water is not less than 70% of the total mass of the aqueous solvent;
the aqueous zinc organic acid/quaternary ammonium salt type ionic liquid contains aqueous zinc organic acid and quaternary ammonium salt type ionic liquid at the same time.
2. The storage-stable, highly weatherable, aqueous ceramic bleeding ink of claim 1, wherein said aqueous zinc organic acid is at least one of zinc acetate, zinc amino acid, zinc picolinate, zinc tartrate, and sodium zinc ethylenediaminetetraacetate.
3. The storage-stable high-weatherability aqueous ceramic bleeding ink according to claim 1, wherein the cation of the quaternary ammonium salt type ionic liquid is imidazolium and its derivative [ R [ ]1R2im]+Or [ R ]1R2R3im]+The anion is Cl－、Br－、BF4－、PF6 －、CF3COO－、C3F7COO－Or CF3SO3 －。
4. The storage-stable, highly weatherable, aqueous ceramic bleeding ink according to claim 1, wherein the water-soluble, small molecule, nitrogen-containing, multidentate complex is at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, hydroxyethylethylenediamine, hydroxyethyldiethylenetriamine, monoethanolamine, diethanolamine, triethanolamine, N-dimethylmonoethanolamine, carbamyl hydrazine, oxalyl hydrazine, disodium ethylenediaminetetraacetate, amino acids, and N-hydroxyethylethylenediaminetriacetic acid.
5. The method for preparing the storage-stable high-weatherability water-based ceramic bleeding ink as claimed in any one of claims 1 to 4, comprising the steps of: uniformly mixing 100 parts by mass of aqueous coloring ink, 0.5-10 parts by mass of aqueous organic acid zinc/quaternary ammonium salt ionic liquid and 0.5-10 parts by mass of water-soluble micromolecule nitrogen-containing polydentate coordination compound at room temperature to obtain the storage-stable high-weatherability aqueous ceramic bleeding ink.
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| CN109021703B (en) * | 2018-08-06 | 2021-08-03 | 佛山科学技术学院 | Bright red ceramic ink-jet pattern penetrating ink and preparation method thereof |
| CN110776769A (en) * | 2019-11-14 | 2020-02-11 | 徐州金港起重机制造有限公司 | Environment-friendly paint suitable for mechanical equipment |
| CN110885573A (en) * | 2019-11-28 | 2020-03-17 | 徐州赛特机械制造有限公司 | Environment-friendly paint for mechanical equipment |
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