CN115259668A - Fluorescent glazing stained paper and preparation method of fluorescent primer layer thereof - Google Patents
Fluorescent glazing stained paper and preparation method of fluorescent primer layer thereof Download PDFInfo
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- CN115259668A CN115259668A CN202210981571.2A CN202210981571A CN115259668A CN 115259668 A CN115259668 A CN 115259668A CN 202210981571 A CN202210981571 A CN 202210981571A CN 115259668 A CN115259668 A CN 115259668A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to the technical field of ceramic decoration, and particularly discloses fluorescent glazing stained paper and a preparation method of a fluorescent primer layer thereof, which are uniform in light emission and improve light efficiency. The preparation method of the fluorescent bottom ink layer comprises the following steps: s1, preparing 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; and S2, printing the ink B on the base paper in a screen printing mode, drying and baking the base paper, sublimating the ink mixing oil, forming a fluorescent space on the surface, scattering a fluorescent agent into the fluorescent space, and leveling. According to the invention, on one hand, the titanium dioxide is used for forming the reflection base layer, so that the surface light effect is improved compared with the stained paper of the titanium dioxide-free reflection base layer, on the other hand, the titanium dioxide is modified to form the organic coating agent outside the titanium dioxide, so that the titanium dioxide is uniformly dispersed in the varnish, no agglomeration exists, the distribution position of the fluorescent agent is controllable, the fluorescent agent of the fluorescent primer layer is uniformly distributed, the continuity of the luminous pattern is strong, and the appearance is attractive and high-brightness.
Description
The application is a divisional application of the invention application named as 'preparation method of fluorescent glazing stained paper and fluorescent ceramic product prepared by the same', the application number of the mother case is 202011422224.3, and the application date of the mother case is as follows: 2020.12.08.
Technical Field
The invention belongs to the technical field of ceramic decoration, and particularly relates to fluorescent glazing stained paper and a preparation method of a fluorescent primer layer thereof.
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 and is combined with the glaze layer to be used as a solvent of the fluorescent material, 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 fluorescent glazing stained paper and a preparation method of a fluorescent primer layer thereof, which have uniform luminescence and improved light efficiency.
In order to solve the technical problems, the invention adopts the technical scheme that:
the preparation method of the fluorescent bottom ink layer is characterized by comprising the following steps:
s1, preparing ink:
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 400-600 meshes, drying the mixture to form 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;
the processing method of the organic coating modified titanium dioxide 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 consists of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5;
s2, preparing a fluorescent bottom ink layer: and (2) screen-printing the ink B obtained in the step (S1) on a piece of base paper, drying, baking at the temperature of 250-350 ℃, sublimating the ink-regulating oil, forming a fluorescent space on the surface, scattering a 600-800-mesh fluorescent agent into the fluorescent space, dispersing the fluorescent agent into the fluorescent space, enabling the fluorescent agent to be attached to titanium dioxide, and leveling.
Preferably, the preparation method of the low-temperature frit in the ink B comprises: 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.
The fluorescent glazing decal paper comprises base paper, a fluorescent primer layer printed and cured on the surface of the base paper, a fluorescent ink layer printed and cured on the fluorescent primer layer and a cover oil layer printed and cured on the fluorescent ink layer, wherein the surface of the fluorescent primer layer is provided with a fluorescent space, fluorescent powder is dispersed in the fluorescent space, the fluorescent primer layer is prepared by the preparation method of claim 1, and the fluorescent primer layer and the fluorescent ink layer are identical in pattern and are arranged in a stacked mode.
Preferably, the preparation method of the fluorescent ink-applying layer comprises the following steps: 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 to stir for 20-40 min by using a three-roller stirrer.
Preferably, the base paper is water-absorbent wood pulp paper with a water-soluble glue layer fully coated on the surface.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a stained paper on glaze, which comprises a fluorescent bottom ink layer, a fluorescent upper ink layer and a cover oil layer, wherein the fluorescent bottom ink layer is prepared by uniformly mixing low-temperature fusion cakes, organic coating modified titanium dioxide, an inorganic pigment and ink mixing oil, then baking at the temperature of 250-350 ℃, sublimating the ink mixing oil, forming a fluorescent space on the surface, and then scattering a fluorescent agent with 600-800 meshes into the fluorescent space to enable the fluorescent agent to be dispersed in the fluorescent space and to be attached to the titanium dioxide, so that the fluorescent agent is dispersed without agglomeration, and the titanium dioxide is arranged around 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%, and the fluorescent agent is zinc copper sulfide, adding water, grinding the mixture in a rapid ball mill to 400-600 meshes, then 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 continuing stirring the mixture 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 frit, 40% of organic coating modified titanium dioxide, water, 400-600 meshes of water, drying into powder, adding varnish which is 20% of the total weight of the powder and takes melamine formaldehyde resin as a binder, stirring uniformly, and continuing stirring for 30min by using a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (2) screen-printing the ink B in the step (S1) on a base paper, wherein the base paper is water-absorbent wood pulp paper with a water-soluble adhesive layer fully coated on the surface, drying, baking at the temperature of 250-350 ℃, sublimating and mixing the ink oil, forming a fluorescent space on the surface, and then scattering a 600-800-mesh fluorescent agent into the fluorescent space to enable the fluorescent agent to be dispersed in the fluorescent space, attached to titanium dioxide and leveled.
S3, preparing a fluorescent ink coating layer: and (3) screen-printing the ink A in the step (S1) on the fluorescent bottom ink layer in 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 layer in the step S3, and drying to obtain the fluorescent over-glaze stained paper, wherein the fluorescent over-glaze stained paper comprises base paper, a fluorescent base ink layer printed and cured on the surface of the base paper, a fluorescent ink layer printed and cured on the fluorescent base ink layer, and a cover oil layer printed and cured on the fluorescent ink layer, fluorescent powder is dispersed in the fluorescent space on the surface of the fluorescent base ink layer, and the fluorescent base ink layer and the fluorescent ink layer have the same pattern and are arranged in a stacked mode.
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 to obtain a mixture uniformly according to the mass percentage, scattering 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 titanium dioxide in the ink B in the step S1 comprises the following steps: 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 400-600 meshes, 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, 15% of zinc white and water are added, the mixture is ground to 400-600 meshes in a rapid ball mill, then the mixture is dried into powder, ink mixing oil which is 15% -25% of the total weight of the powder and takes butyl methacrylate resin as a connecting material is added, the mixture is uniformly stirred, and the mixture is continuously stirred for 40min by a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (2) 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 and mixing the ink oil to form a fluorescent space on the surface, and then scattering a 600-800-mesh fluorescent agent into the fluorescent space to enable the fluorescent agent to be dispersed in the fluorescent space and attached to titanium dioxide for leveling.
S3, preparing a fluorescent ink coating layer: and (3) screen-printing the ink A in the step (S1) on the fluorescent bottom ink layer in 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 (3) screen printing cover oil on the surface of the fluorescent ink coating layer in the step (S3), and drying to obtain the fluorescent glazing decal paper, wherein the fluorescent glazing decal paper comprises base paper, a fluorescent base ink layer printed and cured on the surface of the base paper, a fluorescent ink coating printed and cured on the fluorescent base ink layer, and a cover oil layer printed and cured on the fluorescent ink coating layer, wherein the surface of the fluorescent base ink layer is provided with a fluorescent space, fluorescent powder is dispersed in the fluorescent space, and the fluorescent base ink layer and the fluorescent ink coating layer are identical in pattern and are arranged in a stacked mode.
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 titanium dioxide in the ink B in the step S1 comprises the following steps: 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 400-600 meshes, drying the mixture to form 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, 10% of aluminum powder and water are added, the mixture is ground to 400-600 meshes in a rapid ball mill, then the mixture is dried into powder, ink mixing oil which is 15% -25% of the total weight of the powder and takes melamine formaldehyde resin as a connecting material is added, the mixture is uniformly stirred, and the mixture is continuously stirred for 20min by a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (2) screen-printing the ink B in the step (S1) on a base paper, wherein the base paper is water-absorbent wood pulp paper with a water-soluble adhesive layer fully coated on the surface, drying, baking at the temperature of 250-350 ℃, sublimating and mixing the ink oil, forming a fluorescent space on the surface, and then scattering a 600-800-mesh fluorescent agent into the fluorescent space to enable the fluorescent agent to be dispersed in the fluorescent space, attached to titanium dioxide and leveled.
S3, preparing a fluorescent ink coating layer: and (3) screen-printing the ink A in the step (S1) on the fluorescent bottom ink layer in 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 (3) screen printing cover oil on the surface of the fluorescent ink coating layer in the step (S3), and drying to obtain the fluorescent glazing decal paper, wherein the fluorescent glazing decal paper comprises base paper, a fluorescent base ink layer printed and cured on the surface of the base paper, a fluorescent ink coating printed and cured on the fluorescent base ink layer, and a cover oil layer printed and cured on the fluorescent ink coating layer, wherein the surface of the fluorescent base ink layer is provided with a fluorescent space, fluorescent powder is dispersed in the fluorescent space, and the fluorescent base ink layer and the fluorescent ink coating layer are identical in pattern and are arranged in a stacked mode.
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 titanium dioxide in the ink B in the step S1 comprises the following steps: 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 decal paper, wherein after the blank body and the transparent glaze layer are sintered into a white body at high temperature, the glazing decal 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 400-600 meshes, drying the mixture into powder, adding ink mixing 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 frit, 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 varnish 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 40min by using a three-roller stirrer for later use.
S2, preparing a fluorescent bottom ink layer: and (2) 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 and mixing the ink oil to form a fluorescent space on the surface, and then scattering a 600-800-mesh fluorescent agent into the fluorescent space to enable the fluorescent agent to be dispersed in the fluorescent space and attached to titanium dioxide for leveling.
S3, preparing a fluorescent ink coating layer: and (3) printing the ink A in the step S1 on the fluorescent bottom ink layer in the step S2 in a screen printing mode, and drying, wherein the film forming thickness of the fluorescent top ink layer is smaller than that of the fluorescent bottom ink layer.
S4, preparing fluorescent glazing stained paper: and (3) screen printing cover oil on the surface of the fluorescent ink coating layer in the step (S3), and drying to obtain the fluorescent glazing decal paper, wherein the fluorescent glazing decal paper comprises base paper, a fluorescent base ink layer printed and cured on the surface of the base paper, a fluorescent ink coating printed and cured on the fluorescent base ink layer, and a cover oil layer printed and cured on the fluorescent ink coating layer, wherein the surface of the fluorescent base ink layer is provided with a fluorescent space, fluorescent powder is dispersed in the fluorescent space, and the fluorescent base ink layer and the fluorescent ink coating layer are identical in pattern and are arranged in a stacked mode.
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 titanium dioxide in the ink B in the step S1 comprises the following steps: 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 decal paper, wherein after the blank body and the transparent glaze layer are fired at high temperature to form a white body, the glazing decal 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 (5)
1. The preparation method of the fluorescent bottom ink layer is characterized by comprising the following steps:
s1, preparing ink:
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 400-600 meshes, drying the mixture to form 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;
the processing method of the organic coating modified titanium dioxide 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 consists of maleic anhydride and N, N' -sodium dilauroyl ethylenediamine diacrylate according to the weight ratio of 8: 5;
s2, preparing a fluorescent bottom ink layer: and (2) printing the ink B obtained in the step (S1) on a base paper by silk screen, drying, baking at the temperature of 250-350 ℃, sublimating the ink-adjusting oil, forming a fluorescent space on the surface, scattering a fluorescent agent with 600-800 meshes into the fluorescent space, dispersing the fluorescent agent into the fluorescent space, attaching the fluorescent agent to titanium dioxide, and leveling.
2. The method of making a fluorescent primer layer of claim 1, wherein: the preparation method of the low-temperature frit in 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 prepare the low-temperature clinker.
3. The fluorescent glazing stained paper is characterized in that: the preparation method comprises the following steps of printing and curing a fluorescent bottom ink layer on the surface of a piece of bottom paper, printing and curing a fluorescent inking layer on the surface of the bottom paper, printing and curing a fluorescent inking layer on the fluorescent bottom ink layer, and printing and curing a cover oil layer on the fluorescent inking layer, wherein the surface of the fluorescent bottom ink layer is provided with a fluorescent space, fluorescent powder is dispersed in the fluorescent space, the fluorescent bottom ink layer is prepared by the preparation method of claim 1, and the fluorescent bottom ink layer and the fluorescent inking layer are identical in pattern and are arranged in a stacked mode.
4. The fluorescent overglaze decal paper according to claim 4, wherein: the preparation method of the fluorescent ink-applying layer comprises the following steps: 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 to stir for 20-40 min by using a three-roller stirrer.
5. The fluorescent over-glaze decal paper according to claim 4, wherein: the base paper is water-absorbing wood pulp paper with a water-soluble glue layer fully coated on the surface.
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| 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 |
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