CN117511293A - Reflective watermark ink, reflective watermark ceramic board and preparation method thereof - Google Patents
Reflective watermark ink, reflective watermark ceramic board and preparation method thereof Download PDFInfo
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- CN117511293A CN117511293A CN202410003770.5A CN202410003770A CN117511293A CN 117511293 A CN117511293 A CN 117511293A CN 202410003770 A CN202410003770 A CN 202410003770A CN 117511293 A CN117511293 A CN 117511293A
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- reflective
- watermark
- ink
- mass
- acrylic emulsion
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- 239000000919 ceramic Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011449 brick Substances 0.000 claims abstract description 72
- 239000000839 emulsion Substances 0.000 claims abstract description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
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- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000012466 permeate Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
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- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
-
- 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
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/10—Watermarks
-
- 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
-
- 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
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to reflective watermark ink, a reflective watermark ceramic board and a preparation method thereof, belonging to the technical field of ceramic cold processing. Aiming at the technical problems of obvious reflection texture of ceramic plates or opaque pattern of watermark brick surface, poor flashing effect, high requirements on decorative material performance, purity and firing temperature and unstable production process prepared by the traditional process, the invention provides the reflection watermark ink containing water-based acrylic emulsion, organic silicon polyester resin, nano silicon dioxide, polymethyl methacrylate micro powder, light dispersing agent and the like. When the brick surface pattern is printed, the water-based acrylic emulsion can preferentially permeate and occupy the micro-nano structure on the surface of the ceramic plate, and the organic silicon polyester resin can be attached to the upper layer of the water-based acrylic emulsion and is dehydrated and condensed with acrylic acid to form a whole in the curing process, so that the brick surface pattern has a semi-recessive reflecting effect. The reflective watermark printing ink can be used for preparing the reflective watermark ceramic board with high glossiness and good transparency of the brick surface pattern.
Description
Technical Field
The invention belongs to the technical field of ceramic cold processing, and particularly relates to reflective watermark ink, a reflective watermark ceramic plate and a preparation method thereof.
Background
The ceramic plate is widely applied to the decoration of indoor and outdoor floors and walls due to the characteristics of excellent decorative effect, super durability, easy cleaning, easy treatment and the like. The decoration effects of the brick surface patterns, textures, lines and the like of the traditional ceramic plates are mainly achieved by printing on the surface of a green body or a surface glaze by adopting an ink-jet printing or screen printing technology, then applying the surface glaze or polishing glaze on the brick surface patterns, and performing high-temperature firing, edging, polishing, waxing and the like.
At present, the basic idea of the reflective decorative effect on the surface of the ceramic plate is to find materials with high transmittance and high refractive index, print brick surface patterns or textures, and then burn and polish the materials. However, the reflective texture or brick surface pattern prepared by the process is obvious in opacification, the flashing effect is poor, and meanwhile, the preparation process is high in restriction and can be basically realized only by adopting a screen printing mode. In addition, the requirements on the performance, purity and firing temperature of the material are extremely high, and the production process is extremely unstable.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a reflective watermark ink, a reflective watermark ceramic board and a preparation method thereof, so as to enrich the decoration effect of the ceramic board and enhance the durability of the ceramic tile surface pattern.
In a first aspect, the invention provides a reflective watermarking ink, which is obtained by adding a diluent into a special ink and a curing agent after regular stirring and mixing at a high speed;
the special ink comprises the following components: 25 to 40 parts by mass of aqueous acrylic emulsion, 20 to 30 parts by mass of organic silicon polyester resin, 5 to 10 parts by mass of dispersing agent, 0.1 to 0.5 part by mass of spherical nano silicon dioxide, 2 to 5 parts by mass of polymethyl methacrylate micro powder, 0.1 to 0.5 part by mass of light dispersing agent, 2 to 5 parts by mass of coupling agent and 5 to 10 parts by mass of penetrating agent.
Preferably, the aqueous acrylic emulsion comprises at least one of pure acrylic emulsion, silicone acrylic emulsion, styrene acrylic emulsion or vinyl acetate acrylic emulsion, and the solid content is 45-55 wt%;
the organic silicon polyester resin comprises at least one of polymethyl silicone resin, polyethyl silicone resin and polyaryl silicone resin, and the solid content is 45-55 wt%.
Preferably, the dispersing agent is toluene, xylene or acetone; the particle size of the spherical nano silicon dioxide is 100-300 nm; the grain diameter of the polymethyl methacrylate micropowder is 0.1-2 mu m.
Preferably, the light dispersing agent is an organic silicon resin microsphere with the particle size of 1-5 mu m; the coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane; the penetrating agent is methyl silicone oil or dimethyl silicone oil.
Preferably, the curing agent is at least one of isocyanate or titanium tetraisopropoxide, and the diluent is at least one of petroleum ether, isophorone and cyclohexanone; the mass ratio of the curing agent to the special ink is 1:11-1:7, and the mass ratio of the diluent to the special ink is 1:20-1:5.
Preferably, the conventional stirring speed is 100-300 r/min, and the stirring time is 5-10 min; the high-speed stirring speed is not lower than 2000r/min, and the stirring time is 30-60 min.
In a second aspect, the invention provides a method for preparing a reflective watermark ceramic board, which comprises the following steps: firstly, preprocessing the ceramic tile surface, then printing a tile surface pattern by using the reflective watermark ink, and then curing the printed tile surface pattern to obtain the reflective watermark ceramic board.
Preferably, the pretreatment mode is polishing treatment or plasma activation treatment, and the glossiness of the pretreated brick surface is controlled to be 5-50 ℃;
the pattern printing mode of the brick surface is screen printing or pad printing, and the dosage of the reflective watermark ink is controlled to be 20-50 g/m 2 ；
The brick surface pattern is cured by at least one of electron beam curing or heating curing; wherein the parameters of the electron beam curing include: the voltage is 100-120 KeV, the current is 5-8 mA, the curing time is 1-5 seconds, the heating curing temperature is 100-150 ℃, and the curing time is 5-10 minutes.
Preferably, the preparation method further comprises the step of adopting a combined grinding disc to grind the brick surface pattern flat after the brick surface pattern is solidified;
the combined millstone comprises 5-10 groups of sponge millstones, 5-10 groups of nylon fiber millstones and 5-10 groups of fine wool felt millstones, or 5-10 groups of sponge millstones, 5-10 groups of coarse wool felt millstones and 5-10 groups of fine wool felt millstones; the rotating speed of the grinding disc is 5000-15000 r/min;
the technological parameters of the grinding include: the linear speed of the belt is 18-25 m/min, the brick surface temperature is 60-90 ℃, and the polishing time of each group of grinding disks in the combined grinding disk is 1-3 seconds.
In a third aspect, the invention provides a reflective watermark ceramic board obtained by the preparation method.
Advantageous effects
(1) The invention combines the characteristics of water-based micromolecule emulsion and long-chain polyester resin, takes nano silicon dioxide, PMMA micro powder and light dispersing agent as filling agents, develops special printing ink for ceramic reflective watermarking, has good wear resistance and durability, has excellent adhesive force with ceramic surface, and simultaneously has higher glossiness and excellent transparency;
(2) The ceramic plate with the reflective watermark decorative effect has the characteristics of semi-recessive reflective watermark, the reflective watermark decorative brick surface pattern can be displayed at a specific angle, the reflective effect is excellent, the combination design of the ground color, the burned brick surface pattern and the reflective watermark decorative effect brick surface pattern on the surface of the ceramic plate can be realized, and the decorative effect of the ceramic plate is enriched;
(3) The ceramic plate with the reflective watermark decorative effect developed by the invention has the advantages that the reflective watermark can be selected from lines, brick surface patterns, textures and the like, two-dimensional codes, LOGO and the like, and the semi-recessive decorative function, the anti-counterfeiting function or the indication function of the ceramic plate can be realized at the same time;
(4) The ceramic plate with the reflective watermark decorative effect developed by the invention fully utilizes the physical structures such as micro-nano structures, air holes, pits, grooves and the like on the surface of the ceramic plate, so that the printed reflective watermark brick surface patterns are embedded in the ceramic plate, the adhesive force of the watermark brick surface patterns, lines, textures and the like is increased, and meanwhile, the effects of smooth surface and no convex feeling of the plate can be realized; the process can also be applied to other plate fields, such as marble plates, cement plates, soft porcelain materials, terrazzo plates and the like;
(5) The ceramic plate with the reflective watermark decorative effect, which is developed by the invention, can be prepared by polishing the mature ceramic plate, and is easy to realize mass production.
Drawings
FIG. 1 is a diagram showing the effect of a tile surface of a reflective watermark ceramic board manufactured in example 1 according to the present invention in a side view, wherein the "M" shape is a reflective watermark mark;
FIG. 2 is a microscopic topography of the brick surface around the edge of the reflective watermark mark of the reflective watermark ceramic board manufactured in example 1 of the present invention;
FIG. 3 is a diagram showing the effect of the tile surface of the reflective watermark ceramic board manufactured in example 2 according to the present invention in a side view;
fig. 4 is a graph showing the effect of the tile surface of the reflective watermark ceramic board manufactured in example 3 according to the present invention under a side view.
Detailed Description
The present invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
First, the invention provides a reflective watermarking ink. The reflective watermark ink is prepared by adding a diluent after the special ink and a curing agent are stirred regularly and stirring and mixing at a high speed.
In some embodiments, the composition of the ingredients of the specialty ink include: 25 to 40 parts by mass of aqueous acrylic emulsion, 20 to 30 parts by mass of organic silicon polyester resin, 5 to 10 parts by mass of dispersing agent, 0.1 to 0.5 part by mass of spherical nano silicon dioxide, 2 to 5 parts by mass of polymethyl methacrylate (PMMA) micro powder, 0.1 to 0.5 part by mass of light dispersing agent, 2 to 5 parts by mass of coupling agent and 5 to 10 parts by mass of penetrating agent.
The water-based acrylic emulsion has good water resistance, weather resistance and anti-fouling property, and the polymer structure of the water-based acrylic emulsion is favorable for flowing and wetting of molecular chains on the surfaces of base materials such as ceramics, so that the coating is in close contact with the molecules of the base materials, and the adhesive force is improved; meanwhile, after the film is dried and formed, the film layer is smooth and has high glossiness. In some embodiments, the aqueous acrylic emulsion may include at least one of a pure acrylic emulsion, a silicone acrylic emulsion, a styrene acrylic emulsion, or an vinyl acetate acrylic emulsion; the solid content of the aqueous acrylic emulsion may be 45-55 wt%.
The stability of the ink system can be ensured by controlling the content of the aqueous acrylic emulsion to 25-40 parts by mass. Too high a level can lead to precipitation and thixotropic behaviour of the ink system; too low a content may result in poor printing flow of the ink system.
The film formed by the organic silicon polyester resin has the characteristics of uniformity, compactness, high glossiness, high transparency, high temperature resistance, aging resistance and the like, and the wear resistance of a film layer can be greatly enhanced by compounding the film with inorganic particles. In some embodiments, the silicone polyester resin may include at least one of polymethylsilicone resin, polyethylsilicone resin, and polyarylsilicone resin; the solid content of the silicone polyester resin may be 45 to 55 wt%.
The viscosity of the ink system, the uniformity of film formation and the glossiness can be ensured by controlling the content of the organic silicon polyester resin to 20-30 parts by mass. Too high a content can lead to increased viscosity and poor fluidity of the ink system; too low a content may result in poor film formation uniformity of the ink system.
The invention has the advantages that the water-based acrylic emulsion and the organic silicon polyester resin are compounded for use, so that the water-based acrylic emulsion preferentially permeates and occupies micro-nano structures, air holes, pits or grooves on the surface of the ceramic plate by virtue of small particle size and excellent adhesive force when the ink system is used for printing the brick surface pattern, and meanwhile, the organic silicon polyester resin is adhered to the upper layer of the water-based acrylic emulsion and is integrally formed with acrylic acid through dehydration condensation in the drying and curing process of the whole film layer.
The invention is different from the scene of using the aqueous acrylic emulsion as a glaze adhesive and a dispersing agent, and the main principle of the latter is that the aqueous acrylic emulsion is carbonized at high temperature by utilizing the actions of high-temperature decomposition and molecular chain winding. Moreover, the present invention is also different from the case of using an aqueous acrylic emulsion together with an accelerator for increasing wettability of the ceramic surface to improve adhesion to the ceramic, the main principle of the latter is to utilize physical adsorption of the aqueous acrylic emulsion molecular chain to the ceramic surface and chemical bonding action of the accelerator.
The technical scheme provided by the invention mainly utilizes the small molecule filling property, surface functional groups and transparency of the aqueous acrylic emulsion. Namely, the invention utilizes the filling property of small molecules of the aqueous acrylic emulsion to permeate into the microstructure on the surface of the ceramic, and fills the microstructure to a certain height after solidification, thereby facilitating the post polishing treatment; moreover, the functional groups of the aqueous acrylic emulsion can be condensed with the organic silicon resin to form a whole, so that the strength of the film is improved; meanwhile, the film layer formed by the aqueous acrylic emulsion and the organic silicon resin has good transparency, and can form a semi-recessive light reflecting effect.
In some embodiments, the dispersant may be toluene, xylene, or acetone.
The spherical nano silicon dioxide has high transparency and high hardness, and can strengthen a film layer and enhance wear resistance. In some embodiments, the spherical nano-silica may have a particle size of 100 to 300nm. Too large particle size can result in reduced transparency of the nanoparticle; too small particle size can cause uneven dispersion of the nanoparticles in the ink system, ultimately resulting in reduced abrasion resistance of the ink film.
The transparency and the wear resistance of the ink film layer can be ensured by controlling the content of the spherical nano silicon dioxide to be 0.1 to 0.5 part by mass. Too high a content can result in reduced transparency of the ink film; too low a content may result in insufficient abrasion resistance of the ink film.
The PMMA micro powder has high transmittance and refractive index, has a good scattering effect on light, and can accelerate the curing speed of the ink film. In some embodiments, the particle size of the PMMA micropowder may be 0.1 to 2 μm, transparent grade. Too large a particle size can result in its inability to penetrate into the microstructure of the ceramic substrate surface; too small a particle size may result in poor light scattering or refraction effects of the ink film.
The good light scattering and light refraction effects of the ink film layer can be ensured by controlling the content of PMMA micro powder to 2-5 parts by mass. The excessively high content can cause serious microsphere overlapping, and influence the light scattering and refraction effects of the ink film layer; too low content can also lead to low scattering efficiency of the ink film layer on light, and influence the light reflection effect.
In the technical scheme provided by the invention, the spherical nano silicon dioxide has the main function of increasing the strength of the ink film and ensuring the transparency of the film. The PMMA micro powder has the main functions of enhancing the refraction and scattering of the light by the ink film layer, and is not reflected, and the reflecting effect of the light by the ink film layer in the scheme mainly depends on the subsequent polishing and grinding process. Moreover, nano titanium dioxide or the like cannot be used instead of silica flour in the present solution because nano titanium dioxide has opacity and is amorphous.
The addition of the light dispersing agent can increase the scattering and transmission of the ink film layer to light, and meanwhile, the scattered light can be better and softer and is not dazzling. In some embodiments, the light diffusing agent may be silicone resin microspheres, and the particle size may be 1 to 5 μm. Too large particle size can cause the ceramic plate to be unable to penetrate into the microstructure of the surface of the ceramic plate; too small a particle size may result in poor light diffusion of the ink film.
The light diffusion effect of the ink film layer can be ensured by controlling the content of the light diffusion agent to be 0.1 to 0.5 part by mass. The excessively high content can cause serious agglomeration of the ink system and influence the light diffusion effect of the film layer; too low a content may result in a lower diffusion efficiency of the ink system.
Wherein, the addition of the coupling agent can play a role in increasing the combination force of the printing ink film layer and the ceramic plate. In some embodiments, the coupling agent may be at least one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane.
The coupling effect between the ink system and the ceramic plate can be ensured by controlling the content of the coupling agent to be 2-5 parts by mass. The content is too high, so that the coupling agent is self-crosslinked in the curing process of the printing ink film layer, and the coupling effect is affected; too low content can cause poor coupling effect of the ink system on the ceramic plate, and can not effectively increase the binding force of the film layer and the ceramic plate.
Wherein, the penetrating agent can accelerate the penetration of the printing ink to the microstructure on the surface of the ceramic plate. In some embodiments, the penetrating agent may be methyl silicone oil or dimethyl silicone oil.
The good permeation effect of the ink system on the surface of the ceramic plate can be ensured by controlling the content of the permeation agent to be 5-10 parts by mass. Too high a content can result in a slow curing rate of the ink film; too low a level can result in poor penetration of the ink system into the surface of the ceramic sheet.
In some embodiments, the curing agent may be at least one of isocyanate or titanium tetraisopropoxide; the diluent can be at least one of petroleum ether, isophorone and cyclohexanone.
In some embodiments, the mass ratio of the curing agent to the dedicated ink may be 1:11 to 1:7, preferably 1:10 to 1:7; the mass ratio of the diluent to the special ink can be 1:20-1:5.
The good curing effect and curing efficiency of the ink system can be ensured by controlling the content of the curing agent within a proper range. Too much curing agent can result in a shorter shelf life of the ink system; too little curing agent can result in incomplete curing of the ink film. At the same time, the stability of the ink system can be ensured by controlling the diluent content within a suitable range. The excessive use of the diluent can lead to the decrease of the viscosity of the ink system, lose stability and easily generate precipitation and thixotropic property; too low a diluent amount may result in an inability to activate the ink system and an inability to produce good dilution.
In some embodiments, the speed of the conventional stirring may be 100-300 r/min and the stirring time may be 5-10 min; the high-speed stirring speed is not lower than 2000r/min, and the stirring time can be 30-60 min.
The invention combines the characteristics of water-based micromolecular emulsion and long-chain polyester resin, and develops reflective watermark ink by taking nano silicon dioxide, PMMA micro powder and a light dispersing agent as fillers. The brick surface pattern printed by the ink has good wear resistance, durability and excellent adhesion with the ceramic surface. Meanwhile, the printed brick surface pattern has higher glossiness and excellent transparency.
The following illustrates a preparation method of the reflective watermark ceramic board provided by the invention. The preparation method can comprise the following steps: firstly, preprocessing the ceramic tile surface, then printing a tile surface pattern by using the reflective watermark ink, and then curing the printed tile surface pattern to obtain the reflective watermark ceramic board.
In some embodiments, the pretreatment may be a polishing treatment or a plasma activation treatment; preferably, the glossiness of the brick face after pretreatment can be controlled to be 5-50 degrees. The ceramic tile surface with the glossiness range has rich microstructure and proper depth, and can provide rich ink adhesion sites. The glossiness is too low, the roughness of the brick surface is larger, and the decorative effect and the anti-fouling performance of the brick surface are affected; too high gloss of the tile surface can result in too few ink adhesion sites and insufficient adhesion.
In some embodiments, the tile pattern may be printed in a screen printing (silk screening) or pad printing manner; wherein the dosage of the reflective watermark ink can be controlled to be 20-50 g/m 2 。
In some embodiments, the pattern of tile surfaces may be cured by at least one of electron beam curing or heat curing. Wherein, the parameters of the electron beam curing may include: the voltage is 100-120 KeV, the current is 5-8 mA, and the curing time is 1-5 seconds; the temperature of the heating and curing can be 100-150 ℃ and the curing time can be 5-10 minutes.
It should be noted that the preparation method may further include polishing the brick surface pattern with a combined polishing disc after the brick surface pattern is cured.
In some embodiments, the combined millstone may be a sponge millstone 5-10 group, a nylon fiber millstone 5-10 group, and a fine wool felt millstone 5-10 group, or a sponge millstone 5-10 group, a coarse wool felt millstone 5-10 group, and a fine wool felt millstone 5-10 group; the rotating speed of the grinding disc can be 5000-15000 r/min.
In some embodiments, the flattened process parameters may include: the linear speed of the belt is 18-25 m/min, the brick surface temperature is 60-90 ℃, and the polishing time of each group of grinding discs in the combined grinding disc is 1-3 seconds.
The polishing process is to remove the part of the brick surface pattern higher than the brick surface through polishing and cutting action of the grinding disc, leave the brick surface pattern penetrating into the microstructure part of the brick surface, and form a whole with the brick surface and have the same height as the brick surface.
The invention provides reflective watermark ink based on the thought of organic-inorganic composite materials, and the reflective watermark ink is used for preparing the reflective watermark ceramic board with the reflective watermark decorative effect. The preparation method has simple process, stable process and good durability and wear resistance of the watermark brick surface pattern. The watermark brick surface pattern is reflective and transparent, the decoration effect has semi-invisible characteristics, the watermark is not visible in front view and direct view, and the watermark brick surface pattern can be seen under the condition of light or reflected light at specific angles such as side view, oblique view and the like. Meanwhile, the reflective watermark ceramic board provided by the invention has excellent pollution resistance and chemical corrosion resistance, and the pollution resistance level reaches 5 levels.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the appropriate range from the description herein, and are not intended to be limited to the specific values described below.
Example 1
The preparation method of the reflective watermark ink and the reflective watermark ceramic board provided by the embodiment comprises the following steps:
(1) And (3) preparing reflective watermark ink. The special ink (the composition of the components comprises 25 parts by weight of 45% solid silicone acrylic emulsion, 30 parts by weight of 45% solid silicone polyester resin, 5 parts by weight of dimethylbenzene, 0.1 part by weight of 100nm spherical nano silicon dioxide, 5 parts by weight of 0.1 mu m PMMA micro powder, 0.5 part by weight of 1 mu m silicone resin microsphere, 5 parts by weight of gamma-glycidoxypropyl trimethoxysilane and 10 parts by weight of simethicone) and 11.51 parts by weight of isocyanate curing agent are stirred for 5min at a speed of 100r/min, 8.06 parts by weight of petroleum ether diluent is added, and the mixture is stirred for 40min at a high speed at a speed of 5000r/min.
(2) And (3) preparing the reflective watermark ceramic board. Firstly, polishing the ceramic brick surface and controlling the glossiness of the polished brick surface to be 5 ℃; then, silk-screen printing the brick surface pattern by using the reflective watermark ink prepared in the step (1), and heating and curing the printed brick surface pattern at 150 ℃ for 5min; and then, grinding the brick surface pattern by adopting a combined grinding disc, wherein the combined grinding disc comprises a sponge disc 5 group, a nylon fiber grinding disc 10 group and a fine wool felt grinding disc 10 group, the rotating speed of the grinding disc is 5000r/min, the linear speed of a belt is 25m/min, the brick surface temperature is 60 ℃, and the polishing time of each group of grinding discs in the combined grinding disc is 3 seconds, so that the reflective watermark ceramic plate is prepared.
Fig. 1 is a diagram showing the effect of a tile surface of the reflective watermark ceramic board manufactured in example 1 according to the present invention in a side view, wherein the "M" shape is a reflective watermark mark. It can be seen from the figure that the tile surface exhibits a reflective watermark (M-shaped in the figure) at a side view angle, the mark is distinct, the gloss is high, and the tile surface is embedded, because the reflective watermark tile surface pattern gloss is significantly higher than the surrounding tile surface gloss at a specific angle.
Fig. 2 is a microscopic topography of the brick surface around the edge of the reflective watermark mark of the reflective watermark ceramic board manufactured in example 1 of the present invention. It can be seen from the figure that the reflective watermark mark is different from the surrounding brick surface, the reflective watermark mark is better in shape, flat and compact, and the surrounding brick surface is coarser.
Example 2
The preparation method of the reflective watermark ink and the reflective watermark ceramic board provided by the embodiment comprises the following steps:
(1) And (3) preparing reflective watermark ink. The special ink (the composition of the components comprises 10 parts by weight of 50% solid silicone acrylic emulsion, 20 parts by weight of 55% solid silicone acrylic emulsion, 20 parts by weight of 50% solid silicone polyester resin, 10 parts by weight of dimethylbenzene, 0.5 part by weight of 200nm spherical nano silicon dioxide, 5 parts by weight of 0.5 mu m PMMA micro powder, 0.1 part by weight of 2 mu m silicone resin microsphere, 1 part by weight of gamma-aminopropyl triethoxysilane, 2 parts by weight of gamma-glycidyl ether oxypropyl trimethoxysilane and 5 parts by weight of methyl silicone oil) and 6.91 parts by weight of isocyanate curing agent are stirred for 10 minutes at a speed of 300r/min, and then 13.82 parts by weight of isophorone diluent is added and stirred for 60 minutes at a high speed of 2000 r/min.
(2) And (3) preparing the reflective watermark ceramic board. Firstly, polishing a ceramic brick surface and controlling the glossiness of the polished brick surface to be 50 ℃; then, silk-screen printing the brick surface pattern by using the reflective watermark ink prepared in the step (1), and heating and curing the printed brick surface pattern at 100 ℃ for 10min; and then, adopting a combined millstone to grind the brick surface pattern, wherein the combined millstone comprises a sponge millstone 10 group, a nylon fiber millstone 10 group and a fine wool felt millstone 10 group, the millstone rotating speed is 10000r/min, the belt linear speed is 18m/min, the brick surface temperature is 70 ℃, and the polishing time of each group of millstones in the combined millstone is 2 seconds, so that the reflective watermark ceramic board is prepared.
Fig. 3 is a diagram showing the effect of the tile surface of the reflective watermark ceramic board manufactured in example 2 according to the present invention in a side view. As can be seen from the figure, under the side view angle, the brick surface presents the light-reflecting decorative line similar to stone texture, and the line is approximately silvery, has high glossiness and good light-reflecting effect.
Example 3
The preparation method of the reflective watermark ink and the reflective watermark ceramic board provided by the embodiment comprises the following steps:
(1) And (3) preparing reflective watermark ink. The special ink (the composition of the components comprises 20 parts by mass of 55% solid silicone acrylic emulsion, 20 parts by mass of 45% solid styrene acrylic emulsion, 25 parts by mass of 55% solid silicone polyester resin, 10 parts by mass of toluene, 0.2 part by mass of 300nm spherical nano silicon dioxide, 3 parts by mass of 2 mu m PMMA micro powder, 0.3 part by mass of 5 mu m silicone resin microsphere, 2 parts by mass of gamma-methacryloxypropyl trimethoxysilane and 8 parts by mass of methyl silicone oil) and 11.1 parts by mass of tetraisopropoxy titanium curing agent are stirred for 8min at a speed of 200r/min, and then 4.43 parts by mass of isophorone diluent is added and stirred for 30min at a high speed of 10000 r/min.
(2) And (3) preparing the reflective watermark ceramic board. Firstly, polishing a ceramic brick surface and controlling the glossiness of the polished brick surface to be 25 ℃; then, silk-screen printing the brick surface pattern by using the reflective watermark ink prepared in the step (1), and heating and curing the printed brick surface pattern at 120 ℃ for 6min; and then, adopting a combined millstone to grind the brick surface pattern, wherein the combined millstone comprises a sponge millstone 10 group, a nylon fiber millstone 5 group and a fine wool felt millstone 10 group, the millstone rotating speed is 15000r/min, the belt linear speed is 20m/min, the brick surface temperature is 90 ℃, and the polishing time of each group of millstones in the combined millstone is 1 second, so that the reflective watermark ceramic board is prepared.
Fig. 4 is a graph showing the effect of the tile surface of the reflective watermark ceramic board manufactured in example 3 according to the present invention under a side view. As can be seen from the figure, under the side view angle, the brick surface presents the light-reflecting decorative line similar to stone texture, and the line is approximately silvery, has high glossiness and good light-reflecting effect.
Comparative example 1
The preparation methods of the printing ink and the watermark ceramic board provided in the comparative example refer to the example 1, and the main differences are that: in the step (1), 20 parts by mass of 45% solid silicone-acrylic emulsion and 35 parts by mass of 45% solid silicone polyester resin are adopted.
The ink component adopted in the comparative example has the defects of insufficient filling of the microstructure of the brick surface, defects of the pattern position of the brick surface after polishing and poor light reflection effect due to the fact that the content of the acrylic emulsion and the organic silicon polyester resin in the ink component is improper, the viscosity of an ink system is too high, the ink discharging amount in the printing process is small, and the printing effect is poor.
Comparative example 2
The preparation methods of the printing ink and the watermark ceramic board provided in the comparative example refer to the example 1, and the main differences are that: in the step (1), 45 parts by mass of 45% solid silicone-acrylic emulsion and 10 parts by mass of 45% solid silicone polyester resin are adopted.
The ink composition adopted in the comparative example has the defects of excessively small viscosity of an ink system, unstable system and easy occurrence of precipitation due to improper contents of acrylic emulsion and organic silicon polyester resin. In addition, the ink discharge amount is too large in the printing process, the printing effect is poor, the acrylic emulsion content is too large, the organic silicon polyester resin content is too small, the printed brick surface patterns are blurred in edge, and the polished brick surface patterns are unclear and have poor light reflecting effect.
Comparative example 3
The preparation methods of the printing ink and the watermark ceramic board provided in the comparative example refer to the example 1, and the main differences are that: in the step (1), 30 parts by mass of 45% solid silicon-containing acrylic emulsion and 10 parts by mass of 1 mu m PMMA micro powder are adopted.
Because PMMA micropowder content in the ink component adopted in the comparative example is too large, the PMMA micropowder cannot be effectively dispersed in an ink system, and the agglomeration is serious, and meanwhile, after the later polishing, the refraction and scattering capacity of the printed brick surface pattern on light is weakened, so that the polished brick surface pattern has poor light reflection effect.
The performance test method comprises the following steps:
(1) The gloss of the ceramic panels was tested using a Keshi WGG60-Y4 gloss meter, test index 0.1GU;
(2) The corrosion resistance of the ceramic plate is measured according to GB/T3810.13-2016 chemical resistance, and test items comprise household liquid resistance, chemical reagent resistance, swimming pool salt resistance (100 g/L of ammonium chloride solution and 20mg/L of sodium hypochlorite solution), low concentration resistance (30 g/L of hydrochloric acid solution, citric acid solution and potassium hydroxide solution) and high concentration acid-base resistance (18% hydrochloric acid solution, 5% lactic acid solution and 100g/L of potassium hydroxide solution) and the like.
The test results are shown in tables 1 and 2 below:
TABLE 1 chemical resistance test results
TABLE 2 stain resistance and surface gloss test results
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (10)
1. The reflective watermark ink is characterized in that the reflective watermark ink is obtained by adding a diluent after a special ink and a curing agent are stirred regularly and then stirring and mixing at a high speed;
the special ink comprises the following components: 25 to 40 parts by mass of aqueous acrylic emulsion, 20 to 30 parts by mass of organic silicon polyester resin, 5 to 10 parts by mass of dispersing agent, 0.1 to 0.5 part by mass of spherical nano silicon dioxide, 2 to 5 parts by mass of polymethyl methacrylate micro powder, 0.1 to 0.5 part by mass of light dispersing agent, 2 to 5 parts by mass of coupling agent and 5 to 10 parts by mass of penetrating agent.
2. The reflective watermarking ink according to claim 1, wherein the aqueous acrylic emulsion comprises at least one of pure acrylic emulsion, silicone acrylic emulsion, styrene acrylic emulsion or vinyl acetate acrylic emulsion, and the solid content is 45-55 wt%;
the organic silicon polyester resin comprises at least one of polymethyl silicone resin, polyethyl silicone resin and polyaryl silicone resin, and the solid content is 45-55 wt%.
3. The reflective watermarking ink according to claim 1, wherein the dispersant is toluene, xylene or acetone; the particle size of the spherical nano silicon dioxide is 100-300 nm; the grain diameter of the polymethyl methacrylate micropowder is 0.1-2 mu m.
4. The reflective watermarking ink according to claim 1, wherein the light diffusing agent is a silicone resin microsphere with a particle size of 1-5 μm; the coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane; the penetrating agent is methyl silicone oil or dimethyl silicone oil.
5. The reflective watermarking ink according to claim 1, wherein the curing agent is at least one of isocyanate or titanium tetraisopropoxide, and the diluent is at least one of petroleum ether, isophorone, cyclohexanone; the mass ratio of the curing agent to the special ink is 1:11-1:7, and the mass ratio of the diluent to the special ink is 1:20-1:5.
6. The reflective watermarking ink according to claim 1, wherein the conventional stirring speed is 100-300 r/min and the stirring time is 5-10 min; the high-speed stirring speed is not lower than 2000r/min, and the stirring time is 30-60 min.
7. The preparation method of the reflective watermark ceramic board is characterized by comprising the following steps of: the reflective watermark ceramic board is prepared by firstly preprocessing the ceramic tile surface, then printing the tile surface pattern by using the reflective watermark ink of claim 1, and then curing the printed tile surface pattern.
8. The preparation method according to claim 7, wherein the pretreatment is a polishing treatment or a plasma activation treatment, and the glossiness of the pretreated brick surface is controlled to be 5-50 ℃;
the pattern printing mode of the brick surface is screen printing or pad printing, and the dosage of the reflective watermark ink is controlled to be 20-50 g/m 2 ；
The brick surface pattern is cured by at least one of electron beam curing or heating curing; wherein the parameters of the electron beam curing include: the voltage is 100-120 KeV, the current is 5-8 mA, the curing time is 1-5 seconds, the heating curing temperature is 100-150 ℃, and the curing time is 5-10 minutes.
9. The method of manufacturing according to claim 7, further comprising leveling the tile pattern with a combination abrasive disc after curing the tile pattern;
the combined millstone comprises 5-10 groups of sponge millstones, 5-10 groups of nylon fiber millstones and 5-10 groups of fine wool felt millstones, or 5-10 groups of sponge millstones, 5-10 groups of coarse wool felt millstones and 5-10 groups of fine wool felt millstones; the rotating speed of the grinding disc is 5000-15000 r/min;
the technological parameters of the grinding include: the linear speed of the belt is 18-25 m/min, the brick surface temperature is 60-90 ℃, and the polishing time of each group of grinding disks in the combined grinding disk is 1-3 seconds.
10. A reflective watermarked ceramic sheet material obtainable by the process of claim 7.
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