CN114106591B - Preparation method of special titanium white for high-grade automotive finishing paint - Google Patents
Preparation method of special titanium white for high-grade automotive finishing paint Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K9/00—Use of pretreated ingredients
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Abstract
The application discloses a preparation method of special titanium white for high-grade automotive finishing paint, which comprises the following steps: s1, taking TiO 2 The slurry is screened by a sieve with more than 20 meshes to obtain a first oversize material and a second oversize material; s2, respectively grinding the first oversize material and the first undersize material; s3, sieving the ground material with a sieve of more than 325 meshes to obtain a second undersize material; s4, adding silicate and alkali into the second undersize material, and shearing at a high speed; s5, regulating the pH value of the slurry to 5.5-6.5 within 60-90 min, and homogenizing; s6, coating the slurry with alumina; s7, shearing at a high speed. According to the application, a special grinding mode is adopted to prepare the slurry which has uniform particle size and is free from coarse particles and zirconium ball fragments, and then a high-speed shearing technology and a film forming technology are combined, so that the dispersibility, glossiness and weather resistance of the product are effectively ensured, the energy consumption for later-stage powder preparation is reduced, the production efficiency is improved, and the production cost is reduced.
Description
Technical Field
The application belongs to the technical field of pigment preparation, and particularly relates to a preparation method of titanium white special for high-grade automotive finishing paint.
Background
Titanium dioxide has no toxicity, optimal opacity, optimal whiteness and brightness, is considered as an inorganic white pigment with the best performance in the world at present, accounts for 80 percent of the total white pigment usage, and is widely applied to industries such as paint, plastics, papermaking, printing ink and the like.
The current paint is the largest application industry of titanium dioxide, the titanium dioxide consumed by the paint industry accounts for 55-60% of the total consumption of the titanium dioxide, and the Chinese consumption ratio is about 60-65%. In recent years, with the rapid development of the coating industry, the requirements on the use amount and quality of the coating are continuously improved, the importance of titanium dioxide serving as an important formula in the coating is increasingly remarkable, and the application share is obviously enlarged.
With the acceleration of the life rhythm, the sales of automobiles are increased year by year, the requirements of people on the automobiles are not limited to the riding-replacing tools, and the appearance of the automobiles is more and more concerned, especially the selection of automobile finish. The automotive finish is mainly enamel, has high gloss and better mechanical property and weather resistance. The high-grade automobile and sedan body mainly adopts amino resin, acrylic resin, alkyd resin, polyurethane resin, middle-solid polyester and the like as base materials, inorganic pigments such as titanium white, phthalocyanine pigment, organic pigment with bright color and good weather resistance and the like are selected, and a plurality of auxiliary agents are added to achieve satisfactory appearance and performance. The titanium dioxide is used as the pigment of the automotive finish, the addition amount of the titanium dioxide is generally more than 20%, and the titanium dioxide belongs to one of the types of more titanium dioxide addition amounts of a coating system. The automotive finish has excellent glossiness and weather resistance to titanium dioxide, and most of automotive finishes for automotive manufacturers use imported products and have high price. And many domestic titanium dioxide products have excellent glossiness and poor weather resistance, and good weather resistance and poor glossiness, so that the development of the titanium dioxide with both glossiness and weather resistance has very important significance.
Disclosure of Invention
The application aims to provide a preparation method of titanium white special for high-grade automotive finishing paint, which aims to solve the defects in the prior art.
The application aims at realizing the following technical scheme:
a preparation method of special titanium white for high-grade automotive finishing paint comprises the following steps:
s1, taking TiO 2 The slurry is screened by a sieve with more than 20 meshes to obtain a first oversize material and a second oversize material; the first oversize material accounts for 1.5-5.5% of the total passing material mass;
s2, grinding the first oversize material and the first undersize material in the step S1 to the particle size smaller than 0.35 mu m, wherein the particle size distribution is smaller than 1.50; the first oversize product adopts a circulating grinding mode, and the first undersize product adopts a multi-stage grinding mode;
s3, sieving the materials ground in the step S2 with a sieve with more than 325 meshes to obtain a second oversize material and a second undersize material;
s4, adding silicate and alkali into the second undersize product obtained in the step S3, and carrying out high-speed shearing;
s5, regulating the pH value of the slurry obtained in the step S4 to 5.5-6.5 within 60-90 min, and homogenizing;
s6, coating the slurry obtained in the step S5 with alumina;
s7, shearing the enveloped slurry at a high speed.
Preferably, step S1 TiO 2 The slurry is TiO by a chlorination method 2 The slurry concentration is 350-850 g/L, the screen mesh number is regulated according to the intercepted material quantity, the first oversize material ratio is controlled to be 1.5-5.5%, and the screen mesh number is more than 20 meshes.
Preferably, the step S2 adopts sand grinding, the filling medium is zirconia balls, the zirconia balls are 0.3-0.8 mm in size, the filling rate is 65-90%, the sand grinding rotating speed is 5-15 m/S, and the residence time of the sand grinding material is 5-25 min; and (3) sieving the ground material through a sieve with more than 325 meshes in the step (S3), and continuously grinding the obtained unqualified material, namely the second oversize material.
Preferably, the multi-stage grinding is a two-stage grinding;
the first grinding adopts sand grinding, the filling medium is zirconia balls, the zirconia balls are 0.6-1.8 mm in size, the filling rate is 55-90%, the sand grinding rotating speed is 6-13 m/s, and the residence time of sand grinding materials is 2-15 min; the materials after the first-stage grinding enter a second-stage grinding;
the second-stage grinding adopts sanding, a filling medium is one or two of zirconia balls or zirconium silicate balls, the size of the zirconium balls is 0.3-0.8 mm, the filling rate is 65-85%, the sanding rotating speed is 6-13 m/S, the residence time of sanded materials is 2-15 min, the materials after the second-stage grinding pass through a sieve with more than 325 meshes in the step S3, the obtained qualified materials, namely the second undersize materials, enter the step S3, and the unqualified materials, namely the second oversize materials, return to the step S2 for circular grinding.
Preferably, in the step S4, the silicate is sodium silicate or/and potassium silicate, the alkali is sodium hydroxide and/or potassium hydroxide, the silicate and the alkali are respectively 2.5-3.0% and 0.05-0.1% of the mass of the titanium dioxide in the slurry, and the silicate is calculated by silicon dioxide.
Preferably, the shear rate in the step S4 is 1500-2500 r/min, and the time is 15-25 min.
Preferably, step S5 is carried out at a temperature of 85-98℃and the homogenization time is 20-40 min.
Preferably, the alumina coating conditions in step S6 are as follows: cooling the slurry in the step S5 to 60-75 ℃, and adding an aluminum source and a pH regulator in parallel flow within 60-90 min to keep the pH at 8.5-9.0, wherein the addition amount of the aluminum source is 1.5-2.5% of the mass of titanium dioxide in the slurry based on aluminum oxide; and homogenizing for 20-40 min.
Preferably, the following steps are further included between the step S6 and the step S7:
and regulating the pH value of the slurry to be 5.5-6.5 within 20-30 min, and homogenizing for 20-40 min.
Preferably, the shear rate in the step S7 is 2800-3500 r/min, and the time is 30-45 min.
According to the preparation method of the special titanium white for the high-grade automotive finish, a special grinding mode is adopted to prepare the slurry which is uniform in particle size and free of coarse particles and zirconium ball fragments, influences of the coarse particles and the zirconium ball fragments on glossiness, dispersibility and the like of products are reduced, then a high-speed shearing technology and a film forming technology are combined, firstly, a high-density low-thickness uniform silicon film is coated on the surface of titanium dioxide particles, glossiness and dispersibility of the products are guaranteed, and excellent weather resistance is achieved, finally, an aluminum film is coated, homogenization is carried out on the aluminum film by combining the high-speed shearing technology, soft agglomerate particles are crushed, the dispersibility, glossiness and weather resistance of the products are effectively guaranteed, meanwhile, the later-stage powder preparation energy consumption is reduced, the production efficiency is improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic diagram of a scanning electron microscope of sample 1 obtained in example 1;
FIG. 2 is a schematic diagram of a scanning electron microscope of sample 2 obtained in example 2;
FIG. 3 is a schematic diagram of a scanning electron microscope of sample 3 obtained in example 3;
fig. 4 is a schematic diagram of a scanning electron microscope of comparative sample 1 obtained in comparative example 1.
Detailed Description
The preparation method of the special titanium white for the high-grade automotive finishing paint provided by the application comprises the following steps:
s1, taking titanium dioxide substrate slurry, and sieving the titanium dioxide substrate slurry with a sieve of more than 20 meshes to obtain a first oversize product and a second oversize product; the first oversize material accounts for 1.5 to 5.5 percent of the total passing material mass (the total weight of the first oversize material and the second oversize material);
s2, grinding the first oversize product and the first undersize product in the step S1 respectively until the average grain diameter is less than 0.35 mu m and the grain diameter distribution is less than 1.50; the first oversize material adopts a circulating grinding mode, and the first undersize material adopts a multi-stage grinding mode;
s3, sieving the materials ground in the step S2 with a sieve with more than 325 meshes to obtain a second oversize material and a second undersize material;
s4, adding silicate and alkali into the second undersize product obtained in the step S3, and carrying out high-speed shearing;
s5, regulating the pH value of the slurry obtained in the step S4 to 5.5-6.5 within 60-90 min, and homogenizing;
s6, coating the slurry obtained in the step S5 with alumina;
s7, shearing the enveloped slurry at a high speed.
The applicant finds that large particles (more than or equal to 5 mu m) and small particle numbers (less than or equal to 0.1 mu m particles) in the titanium dioxide have great influence on the glossiness of a paint film, while 0.25-0.35 mu m titanium dioxide particles have great contribution to the covering power of the paint film, and the traditional grinding mode uniformly grinds materials, if the low-strength grinding is adopted, the large particle titanium dioxide accounts for more, so that the glossiness and the covering power of a product are poor, the titanium dioxide can only be used for low-end paint, if the high-strength grinding is adopted, zirconium ball fragment dirt dye is easy to generate, and the large particle titanium dioxide is ground, and meanwhile, more fine particles are ground, so that the proportion of the particles of the titanium dioxide is reduced at 0.25-0.35 mu m, the covering power of the product is poor, and the glossiness of the fine particles is correspondingly poor.
Therefore, the application adopts a special mode of multistage grinding of fine particle materials and independent and strong grinding of large particles for the titanium dioxide substrate slurry in parallel to replace the conventional sanding step, the particle size of the slurry is controlled below 0.35 mu m, titanium dioxide with high concentration of 0.25-0.35 mu m can be obtained, and the luster and the covering power are better; the special grinding mode comprises the steps of firstly sieving titanium dioxide substrate slurry, dividing the titanium dioxide substrate slurry into coarse particle oversize products and fine particle undersize products, and then respectively treating the coarse particle oversize products and the fine particle undersize products, wherein the specific steps are as follows: the coarse particle oversize products are circularly ground until the particle size is below 0.35 mu m, the fine particle undersize products are ground in multiple stages, the titanium dioxide materials are fully and effectively utilized, the defect of insufficient grinding of the coarse particles is effectively prevented, the fine particles are excessively ground, the slurry which has uniform particle size and does not contain zirconium ball fragments and coarse particles is prepared, the problem that the zirconium ball fragments and the coarse particles affect the high gloss and dispersion of titanium dioxide is solved, and the aims of reducing cost and enhancing efficiency are achieved. Through optimization, when the proportion of coarse particles is 1.5-5.5%, the comprehensive efficiency of multistage grinding and cyclic grinding can be improved to the greatest extent.
In general, when a silicon oxide film layer is coated on the surface of titanium dioxide, a part of film layer is adhered to other particles to be deposited together or to be deposited on the surface of agglomerated titanium dioxide base material particles in the deposition process of silicon oxide, so that hard agglomerates which are difficult to open in the subsequent crushing process are caused, the glossiness and the dispersibility of a product are influenced, and meanwhile, the weather resistance of the product is poor due to the non-uniformity of the film layer; according to the application, a layer of silicate micromolecules which are uniformly distributed are pre-adsorbed on the surfaces of titanium dioxide particles by adopting high-speed shearing force, then a slow film forming process in the step S5 is assisted, and a mechanical force homogenizing film layer technology (high-speed shearing after the aluminum film is coated in the step S7) is combined, so that a high-density low-thickness uniform silicon film is formed, and the luster, the dispersibility and the excellent weather resistance of a product are ensured.
After the aluminum film is coated outside the silicon film, the high-speed shearing force is adopted to homogenize the aluminum film, so that the surface film layer of the product is uniform and compact, soft agglomerated particles are crushed, the energy consumption of later-stage powder preparation is reduced, the generation of large particles is avoided, the production efficiency is improved, and the production cost is reduced.
Therefore, the application adopts a special grinding mode to prepare slurry which has uniform particle size and no coarse particle and zirconium ball fragment doping, reduces the influence of coarse particle and zirconium ball fragment on the glossiness, the dispersibility and the like of the product, combines a high-speed shearing technology and a slow film forming technology, firstly coats a high-density low-thickness uniform silicon film on the surface of titanium dioxide particles, ensures the glossiness and the dispersibility of the product and excellent weather resistance, finally coats an aluminum film, and combines the high-speed shearing technology to homogenize the aluminum film and pulverize soft agglomerated particles, thereby effectively ensuring the dispersibility, the glossiness and the weather resistance of the product, simultaneously reducing the later-stage powder preparation energy consumption, improving the production efficiency and reducing the production cost.
Preferably, the titanium dioxide base material slurry in the step S1 is titanium dioxide base material slurry with excellent performance by a chlorination method, the titanium dioxide base material slurry can be pulped and dechlorinated by an oxidation furnace, the concentration of the titanium dioxide base material slurry is 350-850 g/L, the number of the screen meshes is regulated according to the amount of the intercepted materials, the ratio of the first oversize material is controlled to be 1.5-5.5%, and the number of the screen meshes is more than 20 meshes.
The coarse particles are subjected to single-intensity circulating grinding to enable the coarse particles to be effectively and quickly ground into smaller granularity, so that a high-efficiency sand mill is preferably adopted, zirconia balls with smaller size and high filling rate are adopted, grinding strength is enhanced, the particle size of the zirconia balls is further preferably 0.3-0.8 mm, the filling rate is 65-90%, the sanding rotating speed is 5-15 m/S, the residence time of the sanded materials is 5-25 min, the materials after grinding pass through a sieve with more than 325 meshes in the step S3, and the obtained unqualified materials, namely second oversize materials, are continuously ground.
Preferably, the multistage grinding adopts serial two-stage grinding; the first grinding adopts higher strength, the second grinding adopts general strength, and the concrete is:
the first-stage grinding adopts grinding, the filling medium is zirconia balls, the grain diameter of the zirconia balls is 0.6-1.8 mm, the filling rate is 55-90%, the grinding rotating speed is 6-13 m/s, the stay time of the grinding material is 2-15 min, and the material after the first-stage grinding enters the second-stage grinding;
the second grinding adopts sand grinding, the filling medium is one or two of zirconia balls or zirconium silicate balls, the grain diameter of the zirconium balls is 0.3-0.8 mm, the filling rate is 65-85%, the sand grinding rotating speed is 6-13 m/s, and the residence time of the sand grinding material is 2-15 min; and (3) sieving the second-stage ground material through a sieve with more than 325 meshes in the step (S3), wherein the obtained qualified material, namely second undersize material, enters the step (S3), and the unqualified material, namely second oversize material, returns to the step (S2) for cyclic grinding, so that the titanium dioxide material is fully utilized.
Preferably, the silicate in the step S4 is sodium silicate or/and potassium silicate, the alkali is sodium hydroxide and/or potassium hydroxide, and the silicate and the alkali are respectively 2.5-3.0% and 0.05-0.1% of the mass of the titanium dioxide in the slurry, wherein the silicate is calculated by silicon dioxide. The silicate and alkali are preferably added to the slurry in the form of silicate solution and alkali solution, wherein the concentration of silicate solution is 150-200 g/L and the concentration of alkali solution is 280-320 g/L. The addition of a certain amount of alkali in the step can stabilize the slurry added with silicate, improve the dispersibility of the slurry and enable the silicate to be adsorbed on the surface of titanium dioxide particles more easily.
Preferably, the shear rate in the step S4 is 1500-2500 r/min, and the time is 15-25 min.
Preferably, step S5 is carried out at 85-98℃for 20-40 min. The high temperature condition is favorable for the deposition of the silicon oxide film layer.
Preferably, after the step S4 is sheared at a high speed, the slurry is diluted to 200-400 g/L, then the temperature is raised, the pH is regulated, and after the slurry is diluted, the titanium dioxide particles have better dispersibility, so that the silicon oxide film deposition is facilitated.
The alumina coating can be prepared by a conventional coating method, and the application provides a preferable step, which comprises the following steps: cooling the slurry in the step S5 to 60-75 ℃, and adding an aluminum source and a pH regulator in parallel flow within 60-90 min to keep the pH at 8.5-9.0, wherein the addition amount of the aluminum source is 1.5-2.5% of the mass of titanium dioxide in the slurry based on aluminum oxide; and homogenizing for 20-40 min.
Preferably, the following steps are further included between the step S6 and the step S7:
and regulating the pH value of the slurry to be 5.5-6.5 within 20-30 min, and homogenizing for 20-40 min. The slurry after the coating is regulated to be weak acid, which is favorable for water washing and product stability.
Preferably, the shear rate in the step S7 is 2800-3500 r/min, and the time is 30-45 min.
Example 1
Chloride process TiO 2 The slurry with the concentration of 500g/L passes through a 60-mesh vibrating screen, the interception material amount accounts for 4.5% of the total passing material amount, and coarse particle oversize products and fine particle undersize products are obtained; circularly grinding coarse particle oversize materials, wherein a sand mill is filled with zirconia balls with the filling rate of 0.3-0.5 mm, the sand milling rotating speed of 90 percent is 15m/s, the sand milling residence time is 5min, the materials after sand milling pass through a 400-mesh sieve, unqualified materials (400-mesh oversize materials) are continuously ground, and the ground qualified materials (400-mesh undersize materials) enter the next working procedure; fine particle double-stage grinding, wherein the filling rate of a first-stage grinding sand mill is 0.6-1.2 mm, the sand grinding rotating speed is 13m/s, the sand grinding residence time is 2min, the materials after the first-stage grinding enter the second-stage grinding, the materials after the second-stage grinding sand mill are 0.3-0.5 mm, the filling rate of the materials after the second-stage grinding sand mill is 85%, the sand grinding rotating speed is 13m/s, the sand grinding residence time is 2min, the materials after the second-stage grinding pass through a 400-mesh sieve, and the materials after the second-stage grinding are groundPassing qualified (400-mesh screen lower material) materials into a next working procedure, and passing unqualified materials (400-mesh screen upper material) into a coarse particle circulating grinding system; mixing 400-mesh undersize materials, wherein the average grain diameter is 0.320 microns, the grain diameter distribution is 1.48, the undersize materials are qualified, entering a closed high-speed shearing dispersion tank for pretreatment, adding a mixed solution of sodium silicate with the concentration of 150g/L and NaOH with the concentration of 320g/L and the concentration of 0.05%, and carrying out high-speed shearing for 15min at the shearing speed of 1500r/min; pumping the pretreated slurry into a coating tank, adding softened water to dilute the slurry to 300g/L, heating the slurry to 98 ℃, regulating the pH to 5.5 by using a dilute acid solution for 60min, and homogenizing the slurry for 20min; then cooling to 60 ℃, adding 1.5% sodium metaaluminate and dilute acid solution to keep the pH at 8.5, adding for 60min, and homogenizing for 20min; regulating pH to 6.0 with dilute acid solution, adding for 20min, homogenizing for 20min; then pumping the materials into a closed high-speed shearing dispersion tank, and shearing at a shearing speed of 2800r/min for 30min; finally, washing with water, flash evaporating, steam powder and packaging the finished product to obtain a sample 1.
Example 2
Chloride process TiO 2 The slurry passes through a 60-mesh vibrating screen with the concentration of 850g/L, and the interception material quantity accounts for 5.5% of the total passing material quantity, so that coarse particle oversize products and fine particle undersize products are obtained; circularly grinding coarse particle oversize materials, wherein a sand mill is filled with zirconia balls with the filling rate of 0.5-0.8 mm, the sand milling rotating speed of 5m/s and the sand milling residence time of 25min, the materials after sand milling pass through a 600-mesh sieve, unqualified materials continue to be ground, and the ground qualified materials enter the next working procedure; fine particles are ground in two stages, a first-stage grinding sand mill is filled with zirconia balls by 1.0-1.8 mm, the filling rate is 55%, the sand grinding rotating speed is 6m/s, the sand grinding residence time is 15min, and materials after the first-stage grinding enter a second-stage grinding; filling zirconia balls with a secondary grinding sand mill by 0.5-0.8 mm, wherein the filling rate is 65%, the sand grinding rotating speed is 13m/s, and the sand grinding residence time is 2min; the materials after secondary grinding are sieved by a 600-mesh sieve, the materials which are qualified by grinding (600-mesh sieve lower material) enter the next working procedure, and the unqualified materials (600-mesh sieve upper material) enter a coarse particle circulating grinding system; mixing 600 mesh undersize, with average particle diameter of 0.330 μm and qualified particle size distribution of 1.45, pretreating in a sealed high-speed shearing dispersion tank, adding 3.0% sodium silicate solution with concentration of 200g/LMixing the solution with 0.10% NaOH mixed solution with the concentration of 280g/L, and shearing at a high speed for 25min at a shearing speed of 2500r/min; pumping the pretreated slurry into a coating tank, adding softened water to dilute the slurry to 300g/L, heating the slurry to 85 ℃, regulating the pH to 6.5 by using a dilute acid solution for 90min, and homogenizing the slurry for 40min; then cooling to 75 ℃, adding 2.5% sodium metaaluminate and dilute acid solution to keep the pH at 9.0, adding for 90min, and homogenizing for 40min; regulating pH to 6.5 with dilute acid solution, adding for 30min, homogenizing for 40min; then pumping the materials into a closed high-speed shearing dispersion tank, and shearing at a high speed of 3500r/min for 45min; finally, washing with water, flash evaporating, steam powder and packaging the finished product to obtain a sample 2.
Example 3
Chloride process TiO 2 The slurry with the concentration of 650g/L passes through a 40-mesh vibrating screen, the interception material amount accounts for 4.3% of the total passing material amount, and coarse particle oversize products and fine particle undersize products are obtained; circularly grinding coarse particle oversize materials, wherein a sand mill is filled with zirconia balls with the filling rate of 0.5-0.8 mm, the sand milling rotating speed of 8m/s and the sand milling residence time of 17min, the materials after sand milling pass through a 500-mesh sieve, the unqualified materials continue to be ground, and the ground qualified materials enter the next working procedure; fine particles are ground in two stages, a first-stage grinding sand mill is filled with zirconia balls by 1.2-1.6 mm, the filling rate is 69%, the sand grinding rotating speed is 11m/s, the sand grinding residence time is 8min, and materials after the first-stage grinding enter a second-stage grinding; filling zirconia balls with a secondary grinding sand mill with a filling rate of 79 percent and a sand grinding rotating speed of 11m/s for 8min, wherein the filling rate of the zirconia balls is 0.6-0.8 mm; sieving the second-stage ground material with a 500-mesh sieve, enabling the ground qualified (500-mesh undersize) material to enter a next process, and enabling the unqualified material (500-mesh oversize) to enter a coarse particle circulating grinding system; mixing 500 mesh undersize, wherein the average grain diameter is 0.318 micron, the grain diameter distribution is 1.47 qualified, entering a closed high-speed shearing dispersion tank for pretreatment, adding 3.0% sodium silicate solution with the concentration of 200g/L and 0.10% NaOH mixed solution with the concentration of 280g/L, and carrying out high-speed shearing for 25min at the shearing speed of 2500r/min; pumping the pretreated slurry into a coating tank, adding softened water to dilute the slurry to 300g/L, heating the slurry to 90 ℃, regulating the pH to 6.0 by using a dilute acid solution for 80min, and homogenizing the slurry for 30min; then cooling to 65 ℃, adding 2.0% sodium metaaluminate and dilute acid solutionMaintaining pH of the solution at 9.0, adding for 80min, and homogenizing for 30min; adjusting pH to 5.5 with dilute acid solution, adding for 25min, homogenizing for 30min; then pumping the materials into a closed high-speed shearing dispersion tank, and carrying out high-speed shearing at a shearing speed of 3000r/min for 40min; finally, washing with water, flash evaporating, steam powder and packaging the finished product to obtain a sample 3.
Example 4
Chloride process TiO 2 The slurry with the concentration of 570g/L passes through a 80-mesh vibrating screen, the interception material amount accounts for 3.8% of the total passing material amount, and coarse particle oversize products and fine particle undersize products are obtained; circularly grinding coarse particle oversize materials, wherein a sand mill is filled with zirconia balls with the filling rate of 0.3-0.6 mm, the sand milling speed is 7m/s, the sand milling residence time is 16min, the materials after sand milling pass through a 400-mesh sieve, the unqualified materials continue to be ground, and the ground qualified materials enter the next working procedure; fine particles are ground in two stages, a first-stage grinding sand mill is filled with zirconia balls by 0.8-1.2 mm, the filling rate is 65%, the sand grinding rotating speed is 8m/s, the sand grinding residence time is 12min, and materials after the first-stage grinding enter a second-stage grinding; filling zirconium balls by a secondary grinding sand mill with the filling rate of 0.3-0.6 mm, the filling rate of 83%, the sand grinding rotating speed of 8m/s and the sand grinding residence time of 12min; the materials after secondary grinding are sieved by a 400-mesh sieve, the materials which are qualified by grinding (400-mesh sieve lower materials) enter the next working procedure, and the unqualified materials (400-mesh sieve upper materials) enter a coarse particle circulating grinding system; mixing 400-mesh undersize, wherein the average grain diameter is 0.323 micron, the grain diameter distribution is 1.46 qualified, entering a closed high-speed shearing dispersion tank for pretreatment, adding 3.0% sodium silicate solution with the concentration of 200g/L and 0.10% KOH mixed solution with the concentration of 280g/L, and carrying out high-speed shearing for 25min at the shearing speed of 2500r/min; pumping the pretreated slurry into a coating tank, adding softened water to dilute the slurry to 300g/L, heating the slurry to 86 ℃, regulating the pH to 6.0 by using a dilute acid solution for 90min, and homogenizing the slurry for 30min; then cooling to 70 ℃, adding 2.5% sodium metaaluminate and dilute acid solution to keep the pH at 8.7, adding for 90min, and homogenizing for 30min; regulating pH to 6.0 with dilute acid solution, adding for 30min, homogenizing for 40min; then pumping the materials into a closed high-speed shearing dispersion tank, and shearing at a high speed of 3500r/min for 45min; finally, washing, flash evaporation, steam powder and finished product packaging are carried out to obtain a sample 4。
Comparative example 1
Chloride process TiO 2 Slurry with the concentration of 500g/L is subjected to double-stage grinding, a first-stage grinding sand mill fills zirconia balls with the filling rate of 0.6-1.2 mm, the sand grinding rotating speed of 90 percent, the sand grinding residence time of 2min is 13m/s, the second-stage grinding sand mill fills zirconia balls with the filling rate of 85 percent, the sand grinding rotating speed of 13m/s, the sand grinding residence time of 2min, the particle size of the ground material is 0.345 mu m, the particle size distribution is 1.53, the ground material is diluted to 300g/L, the temperature is increased to 98 ℃, 2.5 percent of a mixed solution of sodium silicate with the concentration of 150g/L and NaOH with the concentration of 320g/L is added, the pH value is regulated to 5.5 by a dilute acid solution for 60min, and the homogenization is carried out for 20min; then cooling to 60 ℃, adding 1.5% sodium metaaluminate and dilute acid solution to keep the pH at 8.5, adding for 60min, and homogenizing for 20min; regulating pH to 6.0 with dilute acid solution, adding for 20min, homogenizing for 20min; finally, washing with water, flash evaporation, steam powder and finished product packaging are carried out, and a comparison sample 1 is prepared.
Comparative example and example samples were evaluated for performance
The samples obtained in examples 1 to 4 and comparative example 1 were subjected to production and physical and chemical properties and automotive topcoat system application properties and weather resistance tests by conventional methods, and the results are shown in tables 1 to 3. And scanning electron microscope tests were performed on the samples obtained in examples 1 to 3 and comparative example 1, and the results are shown in fig. 1 to 3.
TABLE 1 sample production data and physicochemical Performance test data
Table 2 sample application Performance test data in automotive topcoat systems
| Sample name | L* | b* | Cover rate | 20° | 60° | 85° |
| Sample 1 | 94.92 | 0.78 | 89.60 | 45.6 | 89.9 | 99.5 |
| Comparative 1 | 94.05 | 1.34 | 84.09 | 23.1 | 68.8 | 89.3 |
| Sample 2 | 95.02 | 0.76 | 89.37 | 46.7 | 89.8 | 100.4 |
| Sample 3 | 94.98 | 0.74 | 89.56 | 50.1 | 89.6 | 100.5 |
| Sample 4 | 95.38 | 0.81 | 89.76 | 54.1 | 89.9 | 100.6 |
Table 3 sample weather resistance test data in automotive topcoat systems
As can be seen from tables 1 to 3, the titanium pigment prepared by the application has extremely high glossiness and weather resistance, high whiteness and high coverage compared with the comparative sample; the scanning electron microscope images shown in figures 1-4 are combined to show that the silicon-aluminum film layer of the titanium dioxide prepared by the application is uniform, compact and continuous, can provide extremely high glossiness and weather resistance when being used for automobile finish paint coating, and solves the problem that the glossiness and the weather resistance are not compatible.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application. It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The preparation method of the special titanium white for the high-grade automotive finishing paint is characterized by comprising the following steps of:
s1, taking TiO 2 The slurry is screened by a sieve with more than 20 meshes to obtain a first oversize material and a second oversize material; the first oversize material accounts for 1.5-5.5% of the total passing material mass;
s2, grinding the first oversize material and the first undersize material in the step S1 to the particle size smaller than 0.35 mu m, wherein the particle size distribution is smaller than 1.50; the first oversize product adopts a circulating grinding mode, and the first undersize product adopts a multi-stage grinding mode;
s3, sieving the materials ground in the step S2 with a sieve with more than 325 meshes to obtain a second oversize material and a second undersize material; the average grain diameter of the second undersize material is 0.318-0.33 mu m, and the grain diameter distribution is 1.45-1.48;
s4, adding silicate and alkali into the second undersize product obtained in the step S3, and carrying out high-speed shearing; the alkali dosage is 0.05 to 0.1 percent of the mass of the titanium dioxide in the slurry; the silicate is sodium silicate or/and potassium silicate, the silicate dosage is 2.5-3.0% of the mass of titanium dioxide in the slurry, and the silicate dosage is calculated by silicon dioxide; the shear rate is 1500-2500 r/min, and the time is 15-25 min;
s5, regulating the pH value of the slurry obtained in the step S4 to 5.5-6.5 within 60-90 min, and homogenizing;
s6, coating the slurry obtained in the step S5 with alumina;
s7, shearing the enveloped slurry at a high speed; the shear rate is 2800-3500 r/min, and the time is 30-45 min.
2. The method for preparing the special titanium white for the high-grade automotive finishing paint according to claim 1, which is characterized in that,
step S1 TiO 2 The slurry is TiO by a chlorination method 2 The slurry concentration is 350-850 g/L, the screen mesh number is regulated according to the intercepted material quantity, the first oversize material ratio is controlled to be 1.5-5.5%, and the screen mesh is used for controllingThe mesh number is more than 20 meshes.
3. The method for preparing the special titanium white for the high-grade automotive finishing paint according to claim 1, which is characterized in that,
step S2, adopting sand grinding, wherein a filling medium is zirconia balls, the zirconia balls are 0.3-0.8 mm in size, the filling rate is 65-90%, the sand grinding rotating speed is 5-15 m/S, and the stay time of sand grinding materials is 5-25 min; and (3) sieving the ground material through a sieve with more than 325 meshes in the step (S3), and continuously grinding the obtained unqualified material, namely the second oversize material.
4. A method for preparing titanium white special for high-grade automotive finishing paint according to claim 1 or 3, wherein,
the multi-stage grinding is double-stage grinding;
the first grinding adopts sand grinding, the filling medium is zirconia balls, the zirconia balls are 0.6-1.8 mm in size, the filling rate is 55-90%, the sand grinding rotating speed is 6-13 m/s, and the residence time of sand grinding materials is 2-15 min; the materials after the first-stage grinding enter a second-stage grinding;
the second-stage grinding adopts sanding, a filling medium is one or two of zirconia balls or zirconium silicate balls, the size of the zirconium balls is 0.3-0.8 mm, the filling rate is 65-85%, the sanding rotating speed is 6-13 m/S, the residence time of sanded materials is 2-15 min, the materials after the second-stage grinding pass through a sieve with more than 325 meshes in the step S3, the obtained qualified materials, namely the second undersize materials, enter the step S3, and the unqualified materials, namely the second oversize materials, return to the step S2 for circular grinding.
5. The method for preparing the special titanium white for the high-grade automotive finishing paint according to claim 1, which is characterized in that,
the alkali in the step S4 is sodium hydroxide and/or potassium hydroxide.
6. The method for preparing the special titanium white for the high-grade automotive topcoat as claimed in claim, wherein the method comprises the steps of,
step S5 is carried out at 85-98 ℃, and the homogenization time is 20-40 min.
7. The method for preparing the special titanium white for the high-grade automotive finishing paint according to claim 1, which is characterized in that,
the alumina coating conditions in the step S6 are as follows: cooling the slurry in the step S5 to 60-75 ℃, and adding an aluminum source and a pH regulator in parallel flow within 60-90 min to keep the pH at 8.5-9.0, wherein the addition amount of the aluminum source is 1.5-2.5% of the mass of titanium dioxide in the slurry based on aluminum oxide; and homogenizing for 20-40 min.
8. The method for preparing the special titanium white for the high-grade automotive finishing paint according to claim 1, which is characterized in that,
the steps between the step S6 and the step S7 further comprise the following steps:
and regulating the pH value of the slurry to be 5.5-6.5 within 20-30 min, and homogenizing for 20-40 min.
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