CN112479590A - Preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by same - Google Patents
Preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by same Download PDFInfo
- Publication number
- CN112479590A CN112479590A CN202011422224.3A CN202011422224A CN112479590A CN 112479590 A CN112479590 A CN 112479590A CN 202011422224 A CN202011422224 A CN 202011422224A CN 112479590 A CN112479590 A CN 112479590A
- Authority
- CN
- China
- Prior art keywords
- fluorescent
- ink
- layer
- temperature
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Wood Science & Technology (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Toxicology (AREA)
- Paper (AREA)
- Printing Methods (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the technical field of ceramic decoration, and particularly discloses a preparation method of fluorescent glazing stained paper and a fluorescent ceramic product prepared by the same, which have uniform luminescence and improved lighting effect. The preparation method of the fluorescent glazing stained paper comprises the following steps: s1, preparation of ink A: weighing low-temperature frit, fluorescent agent and inorganic pigment, adding water, grinding and drying into powder, adding ink mixing oil, and stirring by using a three-roller stirrer; ink B: weighing low-temperature frit, organic coating modified titanium dioxide and inorganic pigment, adding water, grinding and drying into powder, adding ink mixing oil, and stirring by using a three-roller stirrer; s2, screen-printing the ink B obtained in the step S1 on base paper, drying, baking at the temperature of 250-350 ℃, sublimating the ink-mixing oil, forming a fluorescent space on the surface, scattering a fluorescent agent into the fluorescent space, and leveling; printing ink A on the fluorescent bottom ink layer by screen printing, and drying; and (4) screen printing sealing oil on the surface of the fluorescent ink coating layer, and drying.
Description
Technical Field
The invention belongs to the technical field of ceramic decoration, and particularly relates to a preparation method of fluorescent glazing stained paper and a fluorescent ceramic product prepared by the same.
Background
The long-afterglow luminescent material is commonly called luminous powder, comprises zinc copper sulfide or rare earth doped sulfate, has unsaturated energy level in an electronic structure, absorbs photon energy under the illumination condition, enables electrons to generate energy level transition, can release the energy absorbed by the electrons in a darker environment to generate a fluorescent effect, does not have energy consumption and battery hidden danger, does not need to lay a circuit, has good chemical stability, long luminescence time and other excellent physical and chemical properties, and is widely applied to the indication fields of ceramic decoration, building decoration, transportation, fire safety, subway tunnels and the like.
In addition, in the ceramic decoration technology, the over-glaze stained paper is generally adopted, the over-glaze stained paper structure is generally that a layer of ink pattern layer is printed on a base paper, in order to realize the fluorescence effect at the same time, the main components of the ink pattern layer are low-temperature frits, fluorescent materials and varnish, when the ceramic surface is decorated, the ceramic semi-finished product is glazed and fired, then the applique is applied, and the baking is carried out. The varnish is heated to volatilize during baking, and the low-temperature frit melts the solvent serving as the fluorescent material and is combined with the glaze layer, so that the fluorescent pattern layer is attached to the glaze layer. However, the fluorescence efficiency of the fluorescent material is not high, so that the quality of the emitted light needs to be further improved.
Disclosure of Invention
In view of the defects of the prior art, the technical problem to be solved by the invention is to provide a preparation method of fluorescent glazing stained paper and a fluorescent ceramic product prepared by the same, which have uniform luminescence and improved luminous efficiency.
In order to solve the technical problems, the invention adopts the technical scheme that:
the preparation method of the fluorescent glazing stained paper specifically comprises the following steps:
s1, preparing ink:
ink A: weighing 50-70% of low-temperature fusion cake, 20-40% of fluorescent agent and 0-15% of inorganic pigment, adding 100% of the low-temperature fusion cake, the fluorescent agent and the inorganic pigment, adding water, grinding in a rapid ball mill to 400-600 meshes, drying into powder, adding 20-35% of ink adjusting oil of the total weight of the powder, stirring uniformly, and continuing stirring for 20-40 min by using a three-roller stirrer for later use;
ink B: weighing 50-70% of low-temperature frit, 20-40% of organic coating modified titanium dioxide and 0-15% of inorganic pigment, adding 100% of the low-temperature frit, the organic coating modified titanium dioxide and the inorganic pigment, adding water, grinding the mixture in a rapid ball mill to 400-mesh 600-mesh, drying the mixture into powder, adding 15-25% of ink adjusting oil of the total weight of the powder, uniformly stirring the mixture, and continuously stirring the mixture for 20-40 min by using a three-roller stirrer for later use;
s2, preparing a fluorescent bottom ink layer: printing the ink B in the step S1 on a piece of base paper by screen printing, drying, baking at the temperature of 250-350 ℃, sublimating and mixing the ink oil, forming a fluorescent space on the surface, scattering a fluorescent agent with 800 meshes into the fluorescent space, dispersing the fluorescent agent in the fluorescent space, attaching the fluorescent agent to titanium dioxide, and leveling;
s3, preparing a fluorescent ink-applying layer: taking the ink A of the step S1 to be silk-screen printed on the fluorescent bottom ink layer of the step S2, and drying;
s4, preparing fluorescent glazing stained paper: and (5) screen printing sealing oil on the surface of the fluorescent ink coating layer in the step S3, and drying.
Preferably, the method for preparing the low-temperature frits in the ink a and the ink B comprises the following steps: mixing and grinding 15-20% of quartz, 10-15% of feldspar, 20-30% of borax, 15-25% of boric acid, 10-20% of strontium carbonate, 3-5% of nano zinc oxide and 5-8% of kaolin uniformly to prepare a mixture, spreading the mixture into a refractory sagger, and carrying out high-temperature melting at 1250-1320 ℃ to obtain molten slurry; and (3) quenching the slurry with water, cooling and crushing into granules to obtain the low-temperature frit.
Preferably, the fluorescent agent in the ink A is zinc copper sulfide or rare earth doped sulfate.
Preferably, the processing method of the organic coating modified fluorescent agent in the ink B is as follows: putting titanium dioxide into a chloroform solvent with the temperature of 35-45 ℃ for ultrasonic dispersion for 10-20 min, adding a composite organic coating agent for reaction for 4-6 h, wherein the reaction temperature is 50-60 ℃, and the composite organic coating agent is composed of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5.
Preferably, the base paper is water-absorbing wood pulp paper with a water-soluble glue layer fully coated on the surface.
Preferably, the film thickness of the fluorescent ink-applying layer is lower than that of the fluorescent ink-backing layer.
The invention also provides a fluorescent ceramic product which comprises a blank body, a transparent glaze layer and fluorescent glazing stained paper, wherein the blank body and the transparent glaze layer are firstly sintered into a white body at high temperature, the glazing stained paper is stuck on the sintered transparent glaze layer and then sintered together, the sintering temperature is 800-850 ℃, and the sintering time is 3.5-4.5 hours.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an over-glaze stained paper, which comprises a fluorescent primer layer, a fluorescent ink layer and a cover oil layer, wherein the fluorescent primer layer is prepared by uniformly mixing low-temperature fusion cakes, organic coating modified titanium dioxide, inorganic pigments and ink mixing oil, then baking at the temperature of 250-350 ℃, sublimating the ink mixing oil and forming a fluorescent space on the surface, and then scattering a fluorescent agent with the size of 600 plus 800 meshes into the fluorescent space to ensure that the fluorescent agent is dispersed in the fluorescent space and is attached to the titanium dioxide, so that the fluorescent agent is dispersed without agglomeration, and the titanium dioxide is arranged around the fluorescent primer layer, so that on one hand, the titanium dioxide is utilized to form a reflection base layer, the surface light efficiency is improved by 12-18 percent compared with the stained paper without the titanium dioxide reflection base layer, on the other hand, the titanium dioxide is modified outside the organic coating agent to ensure that the titanium dioxide is uniformly dispersed into the ink mixing oil without agglomeration, the luminous pattern has strong continuity, is beautiful and high in brightness, and the continuous luminous time is prolonged by at least 80 min/light storage time of 20min compared with the stained paper without the fluorescent bottom ink layer. In addition, because the fluorescent ink-feeding layer covers the fluorescent ink-backing layer, the pattern is prevented from having small holes or bubbles, the display quality of the luminous pattern is improved, and different ceramic low-temperature pigments can be added according to the requirements to make various different color effects.
Detailed Description
Example 1
The embodiment provides a preparation method of fluorescent glazing decal paper, which specifically comprises the following steps:
s1, preparing ink: ink A: weighing low-temperature frit and fluorescent agent, wherein the low-temperature frit accounts for 65%, the fluorescent agent accounts for 35%, the fluorescent agent is zinc copper sulfide, adding water, grinding in a rapid ball mill to 400-mesh 600-mesh, then drying to powder, adding ink mixing oil which accounts for 20% of the total weight of the powder and takes melamine formaldehyde resin as a connecting material, uniformly stirring, and continuing stirring for 30min by using a three-roller stirrer for later use.
Ink B: weighing low-temperature frit and organic coating modified titanium dioxide, wherein: 60% of low-temperature fusion cake and 40% of organic coating modified titanium dioxide are added with water and ground in a rapid ball mill to 400-600 meshes, then the mixture is dried into powder, 20% of the total weight of the powder and the varnish using melamine formaldehyde resin as a connecting material are added and stirred evenly, and then the mixture is stirred continuously for 30min by a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (4) screen-printing the ink B in the step S1 on a piece of bottom paper, wherein the bottom paper is water-absorbent wood pulp paper with a water-soluble glue layer coated on the surface, drying and baking at the temperature of 250-350 ℃, sublimating the ink-adjusting oil and forming a fluorescence space on the surface, and then scattering the 600-mesh and 800-mesh fluorescent agent into the fluorescence space to enable the fluorescent agent to be dispersed in the fluorescence space and to be attached to titanium dioxide for smoothing.
S3, preparing a fluorescent ink-applying layer: and (4) taking the ink A of the step S1 to screen print on the fluorescent bottom ink layer of the step S2, and drying, wherein the film forming thickness of the fluorescent top ink layer is lower than that of the fluorescent bottom ink layer.
S4, preparing fluorescent glazing stained paper: and S3, screen printing cover oil on the surface of the fluorescent ink-applying layer, and drying to obtain the fluorescent over-glaze stained paper, wherein the fluorescent over-glaze stained paper comprises base paper, the fluorescent ink-applying layer printed and cured on the surface of the base paper, the fluorescent ink-applying layer printed and cured on the fluorescent ink-applying layer, and a cover oil layer printed and cured on the fluorescent ink-applying layer, wherein the surface of the fluorescent ink-applying layer has a fluorescent space and fluorescent powder is dispersed in the fluorescent space, and the fluorescent ink-applying layer have the same pattern and are arranged in a stacked manner.
The preparation methods of the low-temperature frits in the ink a and the ink B in the step S1 are both as follows: mixing and grinding 20% of quartz, 10% of feldspar, 20% of borax, 25% of boric acid, 14% of strontium carbonate, 5% of nano zinc oxide and 6% of kaolin uniformly to obtain a mixture according to the mass percentage, spreading the mixture into a refractory sagger, and carrying out high-temperature melting at 1250-1320 ℃ to obtain molten slurry; and (3) quenching the slurry with water, cooling and crushing into granules to obtain the low-temperature frit.
The processing method of the organic coating modified fluorescent agent in the ink B in the step S1 includes: putting titanium dioxide into chloroform solvent at 40 ℃ for ultrasonic dispersion for 15min, adding a composite organic coating agent for reaction for 4-65 h, wherein the reaction temperature is 55 ℃, and the composite organic coating agent is composed of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5.
The embodiment also provides a fluorescent ceramic product which comprises a blank body, a transparent glaze layer and fluorescent glazing stained paper, wherein the blank body and the transparent glaze layer are sintered at high temperature to form a white body, the glazing stained paper is stuck on the sintered transparent glaze layer and then sintered together, the sintering temperature is 800-830 ℃, and the sintering time is 4 hours.
Example 2
The embodiment provides a preparation method of fluorescent glazing decal paper, which specifically comprises the following steps:
s1, preparing ink: ink A: weighing low-temperature frit, fluorescent agent and zinc white, wherein the low-temperature frit is 50%, the fluorescent agent is 40%, the zinc white is 10%, the fluorescent agent is europium-doped strontium sulfate, adding water, grinding the mixture in a rapid ball mill to 400-mesh and 600-mesh, drying the mixture into powder, adding ink-mixing oil which is 20% of the total weight of the powder and takes melamine-formaldehyde resin as a connecting material, uniformly stirring the mixture, and continuously stirring the mixture for 20min by using a three-roller stirrer for later use.
Ink B: weighing low-temperature frit, organic coating modified titanium dioxide and zinc white, wherein: 65% of low-temperature fusion cake, 20% of organic coating modified titanium dioxide and 15% of zinc white, adding water, grinding the mixture in a rapid ball mill to 400-600 meshes, drying the mixture into powder, adding ink-adjusting oil which is 15-25% of the total weight of the powder and takes butyl methacrylate resin as a connecting material, uniformly stirring the mixture, and continuing stirring the mixture for 40min by using a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (4) screen-printing the ink B in the step S1 on a piece of bottom paper, wherein the bottom paper is water-absorbent wood pulp paper with a water-soluble glue layer coated on the surface, drying and baking at the temperature of 250-350 ℃, sublimating the ink-adjusting oil and forming a fluorescence space on the surface, and then scattering the 600-mesh and 800-mesh fluorescent agent into the fluorescence space to enable the fluorescent agent to be dispersed in the fluorescence space and to be attached to titanium dioxide for smoothing.
S3, preparing a fluorescent ink-applying layer: and (4) taking the ink A of the step S1 to screen print on the fluorescent bottom ink layer of the step S2, and drying, wherein the film forming thickness of the fluorescent top ink layer is lower than that of the fluorescent bottom ink layer.
S4, preparing fluorescent glazing stained paper: and S3, screen printing cover oil on the surface of the fluorescent ink-applying layer, and drying to obtain the fluorescent over-glaze stained paper, wherein the fluorescent over-glaze stained paper comprises base paper, the fluorescent ink-applying layer printed and cured on the surface of the base paper, the fluorescent ink-applying layer printed and cured on the fluorescent ink-applying layer, and a cover oil layer printed and cured on the fluorescent ink-applying layer, wherein the surface of the fluorescent ink-applying layer has a fluorescent space and fluorescent powder is dispersed in the fluorescent space, and the fluorescent ink-applying layer have the same pattern and are arranged in a stacked manner.
The preparation methods of the low-temperature frits in the ink a and the ink B in the step S1 are both as follows: mixing and grinding 15% of quartz, 14% of feldspar, 25% of borax, 18% of boric acid, 20% of strontium carbonate, 3% of nano zinc oxide and 5% of kaolin uniformly to obtain a mixture, spreading the mixture into a refractory sagger, and carrying out high-temperature melting at 1250-1320 ℃ to obtain molten slurry; and (3) quenching the slurry with water, cooling and crushing into granules to obtain the low-temperature frit.
The processing method of the organic coating modified fluorescent agent in the ink B in the step S1 includes: putting titanium dioxide into chloroform solvent at 40 ℃ for ultrasonic dispersion for 20min, adding a composite organic coating agent for reaction for 6 hours at 50 ℃, wherein the composite organic coating agent is composed of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5.
The embodiment also provides a fluorescent ceramic product which comprises a blank body, a transparent glaze layer and fluorescent glazing stained paper, wherein the blank body and the transparent glaze layer are sintered at high temperature to form a white body, the glazing stained paper is stuck on the sintered transparent glaze layer and then sintered together, the sintering temperature is 830-850 ℃, and the sintering time is 3.5 hours.
Example 3
The embodiment provides a preparation method of fluorescent glazing decal paper, which specifically comprises the following steps:
s1, preparing ink: ink A: weighing low-temperature frit, fluorescent agent and aluminum powder, wherein the low-temperature frit accounts for 70%, the fluorescent agent accounts for 20%, the aluminum powder accounts for 10%, the fluorescent agent is zinc copper sulfide, adding water, grinding the mixture in a rapid ball mill to 400-mesh 600-mesh, then drying the mixture into powder, adding ink mixing oil which accounts for 35% of the total weight of the powder and takes melamine formaldehyde resin and butyl methacrylate resin as connecting materials, uniformly stirring the mixture, and continuously stirring the mixture for 35min by using a three-roller stirrer for later use.
Ink B: weighing low-temperature frit, organic coating modified titanium dioxide and aluminum powder, wherein: 70% of low-temperature fusion cake, 20% of organic coating modified titanium dioxide and 10% of aluminum powder, adding water, grinding the mixture in a rapid ball mill to 400-600 meshes, drying the mixture into powder, adding ink mixing oil which is 15-25% of the total weight of the powder and takes melamine formaldehyde resin as a connecting material, uniformly stirring the mixture, and continuously stirring the mixture for 20min by using a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (4) screen-printing the ink B in the step S1 on a piece of bottom paper, wherein the bottom paper is water-absorbent wood pulp paper with a water-soluble glue layer coated on the surface, drying and baking at the temperature of 250-350 ℃, sublimating the ink-adjusting oil and forming a fluorescence space on the surface, and then scattering the 600-mesh and 800-mesh fluorescent agent into the fluorescence space to enable the fluorescent agent to be dispersed in the fluorescence space and to be attached to titanium dioxide for smoothing.
S3, preparing a fluorescent ink-applying layer: and (4) taking the ink A of the step S1 to screen print on the fluorescent bottom ink layer of the step S2, and drying, wherein the film forming thickness of the fluorescent top ink layer is lower than that of the fluorescent bottom ink layer.
S4, preparing fluorescent glazing stained paper: and S3, screen printing cover oil on the surface of the fluorescent ink-applying layer, and drying to obtain the fluorescent over-glaze stained paper, wherein the fluorescent over-glaze stained paper comprises base paper, the fluorescent ink-applying layer printed and cured on the surface of the base paper, the fluorescent ink-applying layer printed and cured on the fluorescent ink-applying layer, and a cover oil layer printed and cured on the fluorescent ink-applying layer, wherein the surface of the fluorescent ink-applying layer has a fluorescent space and fluorescent powder is dispersed in the fluorescent space, and the fluorescent ink-applying layer have the same pattern and are arranged in a stacked manner.
The preparation methods of the low-temperature frits in the ink a and the ink B in the step S1 are both as follows: mixing and grinding 20% of quartz, 10% of feldspar, 30% of borax, 17% of boric acid, 10% of strontium carbonate, 5% of nano zinc oxide and 8% of kaolin uniformly to obtain a mixture according to the mass percentage, spreading the mixture into a refractory sagger, and carrying out high-temperature melting at 1250-1320 ℃ to obtain molten slurry; and (3) quenching the slurry with water, cooling and crushing into granules to obtain the low-temperature frit.
The processing method of the organic coating modified fluorescent agent in the ink B in the step S1 includes: putting titanium dioxide into a chloroform solvent at 45 ℃ for ultrasonic dispersion for 10min, adding a composite organic coating agent for reaction for 6 hours, wherein the reaction temperature is 55 ℃, and the composite organic coating agent is composed of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5.
The embodiment also provides a fluorescent ceramic product which comprises a blank body, a transparent glaze layer and fluorescent glazing stained paper, wherein the blank body and the transparent glaze layer are sintered at high temperature to form a white body, the glazing stained paper is stuck on the sintered transparent glaze layer and then sintered together, the sintering temperature is 800-830 ℃, and the sintering time is 4.5 hours.
Example 4
The embodiment provides a preparation method of fluorescent glazing decal paper, which specifically comprises the following steps:
s1, preparing ink: ink A: weighing low-temperature frit, fluorescent agent and zinc white, wherein the low-temperature frit is 65%, the fluorescent agent is 20%, the zinc white is 15%, the fluorescent agent is zinc copper sulfide, adding water, grinding the mixture in a rapid ball mill to 400-mesh and 600-mesh, then drying the mixture into powder, adding ink adjusting oil which is 30% of the total weight of the powder and takes melamine formaldehyde resin and butyl methacrylate resin as connecting materials, uniformly stirring the mixture, and continuously stirring the mixture for 30min by using a three-roller stirrer for later use.
Ink B: weighing low-temperature frit, organic coating modified titanium dioxide and zinc white, wherein: 50% of low-temperature fusion cake, 40% of organic coating modified titanium dioxide and 10% of zinc white, adding water, grinding the mixture in a rapid ball mill to 400-600 meshes, drying the mixture into powder, adding ink mixing oil which accounts for 20% of the total weight of the powder and takes melamine formaldehyde resin as a connecting material, uniformly stirring the mixture, and continuously stirring the mixture for 40min by using a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (4) screen-printing the ink B in the step S1 on a piece of bottom paper, wherein the bottom paper is water-absorbent wood pulp paper with a water-soluble glue layer coated on the surface, drying and baking at the temperature of 250-350 ℃, sublimating the ink-adjusting oil and forming a fluorescence space on the surface, and then scattering the 600-mesh and 800-mesh fluorescent agent into the fluorescence space to enable the fluorescent agent to be dispersed in the fluorescence space and to be attached to titanium dioxide for smoothing.
S3, preparing a fluorescent ink-applying layer: and (4) taking the ink A of the step S1 to screen print on the fluorescent bottom ink layer of the step S2, and drying, wherein the film forming thickness of the fluorescent top ink layer is lower than that of the fluorescent bottom ink layer.
S4, preparing fluorescent glazing stained paper: and S3, screen printing cover oil on the surface of the fluorescent ink-applying layer, and drying to obtain the fluorescent over-glaze stained paper, wherein the fluorescent over-glaze stained paper comprises base paper, the fluorescent ink-applying layer printed and cured on the surface of the base paper, the fluorescent ink-applying layer printed and cured on the fluorescent ink-applying layer, and a cover oil layer printed and cured on the fluorescent ink-applying layer, wherein the surface of the fluorescent ink-applying layer has a fluorescent space and fluorescent powder is dispersed in the fluorescent space, and the fluorescent ink-applying layer have the same pattern and are arranged in a stacked manner.
The preparation methods of the low-temperature frits in the ink a and the ink B in the step S1 are both as follows: mixing and grinding 18% of quartz, 15% of feldspar, 25% of borax, 15% of boric acid, 16% of strontium carbonate, 5% of nano zinc oxide and 6% of kaolin uniformly to obtain a mixture, spreading the mixture into a refractory sagger, and carrying out high-temperature melting at 1250-1320 ℃ to obtain molten slurry; and (3) quenching the slurry with water, cooling and crushing into granules to obtain the low-temperature frit.
The processing method of the organic coating modified fluorescent agent in the ink B in the step S1 includes: putting titanium dioxide into chloroform solvent at 40 ℃ for ultrasonic dispersion for 15min, adding a composite organic coating agent for reaction for 4 hours, wherein the reaction temperature is 60 ℃, and the composite organic coating agent is composed of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5.
The embodiment also provides a fluorescent ceramic product which comprises a blank body, a transparent glaze layer and fluorescent glazing stained paper, wherein the blank body and the transparent glaze layer are sintered at high temperature to form a white body, the glazing stained paper is stuck on the sintered transparent glaze layer and then sintered together, the sintering temperature is 820-840 ℃, and the sintering time is 4 hours.
The process for manufacturing the fluorescent ceramic products of the embodiments 1 to 4 includes the steps of manufacturing the fluorescent over-glaze decal paper according to the process flows of the embodiments, and then pasting the fluorescent over-glaze decal paper on the white body glaze surface and sintering the white body glaze surface in a kiln. The ceramic product comprises daily ceramics such as cups and pots, ceramic crafts such as vases, ceramic building materials such as ceramic tiles and sanitary wares.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (7)
1. The preparation method of the fluorescent glazing stained paper is characterized by comprising the following steps:
s1, preparing ink:
ink A: weighing 50-70% of low-temperature fusion cake, 20-40% of fluorescent agent and 0-15% of inorganic pigment, adding 100% of the low-temperature fusion cake, the fluorescent agent and the inorganic pigment, adding water, grinding in a rapid ball mill to 400-600 meshes, drying into powder, adding 20-35% of ink adjusting oil of the total weight of the powder, stirring uniformly, and continuing stirring for 20-40 min by using a three-roller stirrer for later use;
ink B: weighing 50-70% of low-temperature frit, 20-40% of organic coating modified titanium dioxide and 0-15% of inorganic pigment, adding 100% of the low-temperature frit, the organic coating modified titanium dioxide and the inorganic pigment, adding water, grinding the mixture in a rapid ball mill to 400-mesh 600-mesh, drying the mixture into powder, adding 15-25% of ink adjusting oil of the total weight of the powder, uniformly stirring the mixture, and continuously stirring the mixture for 20-40 min by using a three-roller stirrer for later use;
s2, preparing a fluorescent bottom ink layer: printing the ink B in the step S1 on a piece of base paper by screen printing, drying, baking at the temperature of 250-350 ℃, sublimating and mixing the ink oil, forming a fluorescent space on the surface, scattering a fluorescent agent with 800 meshes into the fluorescent space, dispersing the fluorescent agent in the fluorescent space, attaching the fluorescent agent to titanium dioxide, and leveling;
s3, preparing a fluorescent ink-applying layer: taking the ink A of the step S1 to be silk-screen printed on the fluorescent bottom ink layer of the step S2, and drying;
s4, preparing fluorescent glazing stained paper: and (5) screen printing sealing oil on the surface of the fluorescent ink coating layer in the step S3, and drying.
2. The method of making fluorescent over-glaze decal paper according to claim 1, wherein: the preparation method of the low-temperature frits in the ink A and the ink B comprises the following steps: mixing and grinding 15-20% of quartz, 10-15% of feldspar, 20-30% of borax, 15-25% of boric acid, 10-20% of strontium carbonate, 3-5% of nano zinc oxide and 5-8% of kaolin uniformly to prepare a mixture, spreading the mixture into a refractory sagger, and carrying out high-temperature melting at 1250-1320 ℃ to obtain molten slurry; and (3) quenching the slurry with water, cooling and crushing into granules to obtain the low-temperature frit.
3. The method of making fluorescent over-glaze decal paper according to claim 1, wherein: the fluorescent agent in the ink A is zinc copper sulfide or rare earth doped sulfate.
4. The method of making fluorescent over-glaze decal paper according to claim 1, wherein: the processing method of the organic coating modified fluorescent agent in the ink B comprises the following steps: putting titanium dioxide into a chloroform solvent with the temperature of 35-45 ℃ for ultrasonic dispersion for 10-20 min, adding a composite organic coating agent for reaction for 4-6 h, wherein the reaction temperature is 50-60 ℃, and the composite organic coating agent is composed of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5.
5. The method of making fluorescent over-glaze decal paper according to claim 1, wherein: the base paper is water-absorbing wood pulp paper with a water-soluble glue layer fully coated on the surface.
6. The method of making fluorescent over-glaze decal paper according to claim 1, wherein: the film forming thickness of the fluorescent ink-applying layer is lower than that of the fluorescent bottom ink layer.
7. A fluorescent ceramic article, characterized in that: the fluorescent over-glaze stained paper consists of a blank body, a transparent glaze layer and the fluorescent over-glaze stained paper as claimed in any one of claims 1 to 6, wherein after the blank body and the transparent glaze layer are sintered into a white body at high temperature, the over-glaze stained paper is stuck on the sintered transparent glaze layer and then sintered together, the sintering temperature is 800-850 ℃, and the sintering time is 3.5-4.5 hours.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210981571.2A CN115259668B (en) | 2020-12-08 | 2020-12-08 | Fluorescent glazed stained paper and preparation method of fluorescent bottom ink layer thereof |
| CN202011422224.3A CN112479590B (en) | 2020-12-08 | 2020-12-08 | Preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011422224.3A CN112479590B (en) | 2020-12-08 | 2020-12-08 | Preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210981571.2A Division CN115259668B (en) | 2020-12-08 | 2020-12-08 | Fluorescent glazed stained paper and preparation method of fluorescent bottom ink layer thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112479590A true CN112479590A (en) | 2021-03-12 |
| CN112479590B CN112479590B (en) | 2022-09-13 |
Family
ID=74940700
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011422224.3A Active CN112479590B (en) | 2020-12-08 | 2020-12-08 | Preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by same |
| CN202210981571.2A Active CN115259668B (en) | 2020-12-08 | 2020-12-08 | Fluorescent glazed stained paper and preparation method of fluorescent bottom ink layer thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210981571.2A Active CN115259668B (en) | 2020-12-08 | 2020-12-08 | Fluorescent glazed stained paper and preparation method of fluorescent bottom ink layer thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN112479590B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105215A (en) * | 2021-03-31 | 2021-07-13 | 扬州工业职业技术学院 | Fluorescent ceramic material for illumination |
| CN113698233A (en) * | 2021-08-31 | 2021-11-26 | 深圳市国瓷永丰源瓷业有限公司 | Pearlescent interference color combination product and preparation method thereof, stained paper and one-time color firing process |
| CN113954562A (en) * | 2021-10-13 | 2022-01-21 | 广东健诚高科玻璃制品股份有限公司 | Heat transfer decal paper for automatic applique machine and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865591A (en) * | 2006-06-01 | 2006-11-22 | 潮州市西湖瓷花纸有限公司 | Method for making paper for used in embossed and patterned gold porcelain |
| CN103287669A (en) * | 2012-03-02 | 2013-09-11 | 湖南富强特种陶瓷制造有限公司 | Method for producing high-temperature-resistant fluorescent anti-counterfeiting mark |
| CN106758685A (en) * | 2017-02-28 | 2017-05-31 | 四川杰邦科技有限公司 | A kind of reflective ceramic tile in diffusing reflection tunnel and preparation method thereof |
| CN109824384A (en) * | 2019-04-15 | 2019-05-31 | 淄博丰之源贸易有限公司 | The ceramics preparation method and decal method of fluorescence embossment marble paper |
| CN110437834A (en) * | 2019-10-10 | 2019-11-12 | 佛山市钜亮光学材料有限公司 | A kind of method of the preparation method of the high fluorescent powder of thermal stability and production Ceramic Tiles |
| CN110684373A (en) * | 2019-10-25 | 2020-01-14 | 邵天山 | Pre-dispersed composite titanium dioxide and preparation method thereof |
| CN111607258A (en) * | 2020-06-09 | 2020-09-01 | 安徽昂然节能环保科技有限公司 | Self-luminous decal paper for underglaze and printing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135569A (en) * | 1990-08-24 | 1992-08-04 | W. R. Grace & Co.-Conn. | Ink composition containing fluorescent component and method of tagging articles therewith |
| CN1375528A (en) * | 2001-03-19 | 2002-10-23 | 樊官保 | Photochromic ink compound and its application |
| US8974590B2 (en) * | 2003-12-18 | 2015-03-10 | The Armor All/Stp Products Company | Treatments and kits for creating renewable surface protective coatings |
| CN108299924A (en) * | 2017-08-13 | 2018-07-20 | 安徽康瑞高科新材料技术工程有限公司 | A kind of white paint and preparation method thereof brightened |
-
2020
- 2020-12-08 CN CN202011422224.3A patent/CN112479590B/en active Active
- 2020-12-08 CN CN202210981571.2A patent/CN115259668B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865591A (en) * | 2006-06-01 | 2006-11-22 | 潮州市西湖瓷花纸有限公司 | Method for making paper for used in embossed and patterned gold porcelain |
| CN103287669A (en) * | 2012-03-02 | 2013-09-11 | 湖南富强特种陶瓷制造有限公司 | Method for producing high-temperature-resistant fluorescent anti-counterfeiting mark |
| CN106758685A (en) * | 2017-02-28 | 2017-05-31 | 四川杰邦科技有限公司 | A kind of reflective ceramic tile in diffusing reflection tunnel and preparation method thereof |
| CN109824384A (en) * | 2019-04-15 | 2019-05-31 | 淄博丰之源贸易有限公司 | The ceramics preparation method and decal method of fluorescence embossment marble paper |
| CN110437834A (en) * | 2019-10-10 | 2019-11-12 | 佛山市钜亮光学材料有限公司 | A kind of method of the preparation method of the high fluorescent powder of thermal stability and production Ceramic Tiles |
| CN110684373A (en) * | 2019-10-25 | 2020-01-14 | 邵天山 | Pre-dispersed composite titanium dioxide and preparation method thereof |
| CN111607258A (en) * | 2020-06-09 | 2020-09-01 | 安徽昂然节能环保科技有限公司 | Self-luminous decal paper for underglaze and printing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵田贵等: "高反射白色釉料的应用概述", 《陶瓷》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105215A (en) * | 2021-03-31 | 2021-07-13 | 扬州工业职业技术学院 | Fluorescent ceramic material for illumination |
| CN113698233A (en) * | 2021-08-31 | 2021-11-26 | 深圳市国瓷永丰源瓷业有限公司 | Pearlescent interference color combination product and preparation method thereof, stained paper and one-time color firing process |
| CN113954562A (en) * | 2021-10-13 | 2022-01-21 | 广东健诚高科玻璃制品股份有限公司 | Heat transfer decal paper for automatic applique machine and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115259668A (en) | 2022-11-01 |
| CN115259668B (en) | 2023-06-27 |
| CN112479590B (en) | 2022-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112479590B (en) | Preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by same | |
| US11001534B2 (en) | Semi-transparent ceramic sheet decorated with ink light-absorbance and preparation method thereof | |
| CN100478308C (en) | Ru china shining glaze and its preparation method | |
| CN109824384A (en) | The ceramics preparation method and decal method of fluorescence embossment marble paper | |
| CN106830685A (en) | A kind of glaze compositions | |
| CN107032832A (en) | A kind of Ceramic Tiles with color changeable effect and preparation method thereof | |
| CN107417114A (en) | Luminescence generated by light cover-coat enamel, luminescent microcrystal Ceramic Tiles and preparation method thereof | |
| CN107140947A (en) | A kind of surface has the pottery and its preparation technology of noctilucence spot | |
| CN106396638A (en) | Low-temperature lightweight lime gradient glaze ceramic and production process thereof | |
| CN110919831A (en) | Energy-storage luminous ceramic tile and preparation method thereof | |
| CN103835465B (en) | A kind of long-afterglow fluorescent Ceramic Tiles | |
| CN111607258A (en) | Self-luminous decal paper for underglaze and printing method thereof | |
| CN108658463B (en) | Fluorescent glaze, ceramic product prepared from fluorescent glaze and method for preparing ceramic product | |
| CN101209930A (en) | Luminous ceramic and preparing process thereof | |
| CN113754411A (en) | Preparation method of 3D printing red overglaze Ce: YAG fluorescent ceramic | |
| CN103896633B (en) | A kind of manufacture method of long-afterglow fluorescent ceramic tile | |
| CN110240472B (en) | Multi-color light-storage ceramic for fire indication and preparation method thereof | |
| CN112010673A (en) | Luminous ceramic tile and preparation method thereof | |
| CN114249586B (en) | Black ceramic tile with three-dimensional flashing effect and preparation method thereof | |
| CN109836042A (en) | A kind of insulation luminescent ceramic brick and preparation method thereof | |
| CN113087503A (en) | Once-fired luminescent ceramic tile and preparation method thereof | |
| KR200426648Y1 (en) | Photoluminescent Tile | |
| CN113968752A (en) | Anti-counterfeiting ceramic tile and preparation method thereof | |
| CN111777332A (en) | Noctilucent glaze, noctilucent ceramic and preparation method thereof | |
| CN101591529B (en) | Process method for anti-ultraviolet film coating of zinc sulfide luminescent powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |