CN103013184A - Preparation method of special type titanium dioxide pigment for plastic color master batch - Google Patents
Preparation method of special type titanium dioxide pigment for plastic color master batch Download PDFInfo
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Abstract
The invention provides a preparation method of a special type titanium dioxide pigment for a plastic color master batch, comprising the following steps of: preparing a titanium dioxide primary product into titanium dioxide slurry; adjusting a pH (Potential of Hydrogen) value by using an alkaline solution; adding phosphate or phosphoric acid, dispersing and carrying out grinding treatment; heating and raising the temperature; adding an acidic aluminum salt compound or an alkaline aluminum salt compound; meanwhile, adding inorganic acid or inorganic alkali and maintaining the pH value of the slurry; curing to form a first layer of a hydrated alumina covering layer on the surface of a titanium dioxide particle; continuously adding the inorganic acid or the inorganic alkali, adjusting the pH value and curing; washing by using de-ionized water and filtering; adding modified polysiloxane into a filtering cake; dispersing at a high speed to form a second layer of an organic silicon covering layer on the hydrated alumina covering layer; and drying and carrying out air-powder treatment to obtain the special type titanium dioxide pigment for the plastic color master batch. The preparation method disclosed by the invention has the advantages that the combination property is good; the dry powder mobility, the dispersity, the covering capability, the machining plasticization performance, the light resistance and the heat resistance achieve the level of special titanium dioxide for an international color master batch; and the application prospect is wide.
Description
Technical field
The present invention relates to a kind of preparation method of plastic color master grain tailored version TiO 2 pigment.
Background technology
Titanium dioxide is the important fine chemical material of chemical industry, light industry industry.Because titanium dioxide has the performances such as refractive index is high, strong coloring force, glossiness is good, whiteness is high, dispersiveness is strong, weathering resistance is strong, be described as " king of white pigment ", therefore, by extensively should be owing in the industrial production such as coating, plastics, papermaking, rubber, man-made fiber.Along with the fast development of China's plastics industry, the especially development of the industries such as automobile, household electrical appliance and daily necessities, people further improve articles colored requirement, and the painted main colorize method that has become plastics of Masterbatch is widely used.
Titanium dioxide is hydroaropic substance, and it easily is difficult for wetting by non-polar material by water-wet.Plastics belong to typical non-polar compound, improve compatibility consistency and the dispersiveness of titanium dioxide and plastics, must carry out hydrophobicity to titanium dioxide and process.
CN1189178A discloses a kind of durable pigments for plastics, by the aluminium film to the various forms of coated by titanium dioxide, effectively improves opacity and the opacifying power of product.But the dry powder of this series products is mobile, dispersiveness and processing plasticizing performance can't satisfy the requirement that use in plastic color master grain field.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of high covering power that has, and has the preparation method of the plastic color master grain special titanium pigment of excellent dry powder flowability, dispersiveness and processing plasticizing performance.
Technical solution of the present invention is:
A kind of preparation method of plastic color master grain tailored version TiO 2 pigment, its concrete steps are as follows:
1, adopt chlorination process rutile titanium dioxide first product, add the titania slurry that a certain amount of deionized water is mixed with concentration 500g/L～800g/L, alumina content is 0.22 μ m～0.25 μ m at 0.6%～1.2%, D50 in the described titanium dioxide first product; Regulating titania slurry pH value with basic solution is 9.0～11.0, add component A, disperse 20min～30min, described component A is at least a in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid, wherein, Vanadium Pentoxide in FLAKES accounts for titanium dioxide first product weight and counts 0.1%～0.5% among the component A;
2, the titania slurry that disperses is carried out milled processed, and from water slurry, remove grinding medium;
3, the slurry after will grinding is heated to 50 ℃～80 ℃, and keeps this temperature in whole coating process;
4, in 0.5h～3h, add B component, described B component is acid aluminium salt compound or basic aluminium salt compound, described acid aluminium salt compound is at least a in Tai-Ace S 150, the aluminum chloride, described basic aluminium salt compound is at least a in sodium metaaluminate, the potassium metaaluminate, wherein, aluminum oxide accounts for titanium dioxide first product weight and counts 1.0%～3.0% in the B component; Simultaneously, by adding mineral acid or mineral alkali, keeping slurry pH is 5～10, and slaking 0.5h～2h forms the first layer hydrated aluminum oxide coating layer on the TiO 2 particles surface;
5, continue to add mineral acid or mineral alkali, regulating the titania slurry pH value that coats hydrated aluminum oxide is 6～8, slaking 1h～2h;
6, will regulate titania slurry after the pH value with 50 ℃～80 ℃ deionization washing, filter, be washed till filter cake specific conductivity＞15000 Ω cm;
7, in filter cake, add Siloxane-Oxyalkylene Copolymers and amino-long chain alkane comodified polysiloxane mixture, add-on counts 0.2%～1.5% with titanium dioxide first product weight, then under 1500rpm～2000 rpm, carry out high speed dispersion 30min～120min, so that form second layer silicone covering layer at the hydrated aluminum oxide coating layer, dry, gas powder is processed, and makes plastic color master grain tailored version TiO 2 pigment.
The mass ratio of Siloxane-Oxyalkylene Copolymers and amino-long chain alkane comodified polysiloxane is 0.5:1～3:1 in the described mixture.
The concentration of described component A solution is with P
2O
5Count 50g/L～200g/L.
The concentration of described B component solution is with Al
2O
3Count 80 g/L～200g/L.
After the milled processed, titania slurry particle diameter D50 is 300nm～400nm, D90＜700nm.
Described component A is a kind of in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid.
Described component A is two kinds in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid.
Mineral acid described in step 4, the step 5 is at least a in hydrochloric acid, sulfuric acid, the nitric acid.
Mineral alkali described in step 4, the step 5 is at least a in sodium hydroxide, the potassium hydroxide.
The titanium dioxide first product that the present invention adopts chlorination process to produce, the particle shape of its product is near ball-type, size distribution is narrower, particle diameter is thinner, phase of the aobvious blue end, process aluminium inorganic coating forms the alumina-coated layer and the organosilicon organic process forms the organosilicon coating layer, and vigorous nurse type aluminum oxide, pseduo-boehmite type aluminum oxide that the alumina-coated layer forms are conducive to improve the dispersing property of titanium dioxide and shield the photochemical activity of titanium dioxide; Organic surface-treated effect mainly improves titanium dioxide in compatible compatibleness and the dispersiveness of coloring plastic Application Areas, the high comprehensive performance of the plastic color master grain tailored version TiO 2 pigment for preparing, in plastic color master grain field, the indexs such as its dry powder flowability, dispersiveness, opacifying power, processing plasticizing performance, photostabilization and thermotolerance reach the level of international Masterbatch special titanium pigment, are with a wide range of applications.
Embodiment
Embodiment 1
1, take by weighing that alumina content is 0.6%, D50 is the chlorination process rutile titanium dioxide first product powder 400g of 0.22 μ m, add the titania slurry that the 800mL deionized water is mixed with, whole coating process adopts pH meter test slurry pH value; Regulate slurry pH to 9.0 with sodium hydroxide solution, add sodium hexametaphosphate solution 8mL, the concentration of sodium hexametaphosphate solution is with P
2O
5Count 50g/L, disperse 20min;
2, the titania slurry that disperses is carried out milled processed, after the milled processed, titania slurry particle diameter D50 is that 350nm, D90 are 620nm, removes grinding medium from water slurry;
3, the slurry after will grinding is heated to 50 ℃, and keeps this temperature in whole coating process;
4, add sodium metaaluminate and potassium metaaluminate aluminum mixture salts solution 100mL in 0.5h, the concentration of sodium aluminate solution and potassium metaaluminate solution is with Al
2O
3Meter is 80 g/L, adds simultaneously mass percent concentration and be 20% hydrochloric acid soln, keeps slurry pH to 5, and slaking 60min forms the first layer hydrated aluminum oxide coating layer on the TiO 2 particles surface;
5, the adding mass percent concentration is 20% sodium hydroxide solution, regulates the titania slurry pH value to 8 that coats hydrated aluminum oxide, slaking 60min;
6, will regulate titania slurry after the pH value with 50 ℃ deionized water washing, and filter, being washed till the filter cake specific conductivity is 16000 Ω cm;
7, in filter cake, add 1.0g Siloxane-Oxyalkylene Copolymers and 1.0g amino-long chain alkane comodified polysiloxane, under 1500rpm, carry out high speed dispersion 2h, so that form second layer silicone covering layer at the hydrated aluminum oxide coating layer, dry, gas powder is processed, and makes plastic color master grain tailored version TiO 2 pigment.
Embodiment 2
1, takes by weighing that alumina content is 0.9%, D50 is the chlorination process rutile titanium dioxide first product powder 400g of 0.24 μ m, add the 700mL deionized water and be mixed with titania slurry, whole coating process adopts pH meter test slurry pH value, regulate slurry pH to 10.0 with sodium hydroxide solution, add sodium pyrophosphate solution 8mL, the concentration of sodium pyrophosphate solution is with P
2O
5Count 150g/L, disperse 25min;
2, the titania slurry that disperses is carried out milled processed, after the milled processed, titania slurry particle diameter D50 is that 300nm, D90 are 600nm, removes grinding medium from water slurry;
3, the slurry after will grinding is heated to 60 ℃, and keeps this temperature in whole coating process;
4, add sodium aluminate solution 53mL in 1.0h, the concentration of sodium aluminate solution is with Al
2O
3Count 150g/L, simultaneously, the adding mass percent concentration is 20% hydrochloric acid soln, keeps slurry pH to 8, and slaking 30min forms the first layer hydrated aluminum oxide coating layer on the TiO 2 particles surface;
5, the adding mass percent concentration is 20% sodium hydroxide solution, regulates the titania slurry pH value to 7 that coats hydrated aluminum oxide, slaking 90min;
6, will regulate titania slurry after the pH value with 70 ℃ deionized water washing, and filter, being washed till the filter cake specific conductivity is 18000 Ω cm;
7, in filter cake, add 0.8g Siloxane-Oxyalkylene Copolymers and 1.6g amino-long chain alkane comodified polysiloxane, under 1700rpm, carry out high speed dispersion 1.5h, so that form second layer silicone covering layer at the hydrated aluminum oxide coating layer, dry, gas powder is processed, and makes plastic color master grain tailored version TiO 2 pigment.
Embodiment 3
1, takes by weighing that alumina content is 1.2%, D50 is the chlorination process rutile titanium dioxide first product powder 400g of 0.25 μ m, add the 600mL deionized water and be mixed with titania slurry, whole coating process adopts pH meter test slurry pH value, regulate slurry pH to 10.0 with sodium hydroxide solution, add trisodium phosphate and tertiary sodium phosphate mixed phosphate salts solution 12mL, the concentration of sodium pyrophosphate solution and trisodium phosphate solution is with P
2O
5Meter is 100g/L, disperses 20min;
2, the titania slurry that disperses is carried out milled processed, after the milled processed, titania slurry particle diameter D50 is that 360nm, D90 are 680nm, removes grinding medium from water slurry;
3, the slurry after will grinding is heated to 70 ℃, and keeps this temperature in whole coating process;
4, add aluminum trichloride solution 33mL in 1.5h, the concentration of aluminum trichloride solution is with Al
2O
3Count 120 g/L; Add simultaneously mass percent concentration and be 20% sodium hydroxide solution, keep slurry pH to 6, slaking 90min forms the first layer hydrated aluminum oxide coating layer on the TiO 2 particles surface;
5, continuation adding mass percent concentration is 20% sodium hydroxide solution, regulates the titania slurry pH value to 7 that coats hydrated aluminum oxide, slaking 60min;
6, will regulate titania slurry after the pH value with 70 ℃ deionized water washing, and filter, being washed till the filter cake specific conductivity is 24000 Ω cm;
7, in filter cake, add 0.6g Siloxane-Oxyalkylene Copolymers and 0.2g amino-long chain alkane comodified polysiloxane, under 1900rpm, carry out high speed dispersion 1h, so that form second layer silicone covering layer at the hydrated aluminum oxide coating layer, dry, gas powder is processed, and makes plastic color master grain tailored version TiO 2 pigment.
Embodiment 4
1, take by weighing that alumina content is 1.0%, D50 is the chlorination process rutile titanium dioxide first product powder 400g of 0.23 μ m, add the 500mL deionized water and be mixed with titania slurry, whole coating process is adopted pH meter test slurry pH value; Regulate slurry pH to 11.0 with sodium hydroxide solution, add phosphoric acid solution 10mL, the concentration of phosphoric acid is with P
2O
5Count 200g/L, disperse 30min;
2, the titania slurry that disperses is carried out milled processed, after the milled processed, titania slurry particle diameter D50 is that 400nm, D90 are 580nm, removes grinding medium from water slurry;
3, the slurry after will grinding is heated to 80 ℃, and keeps this temperature in whole coating process;
4, add alum liquor 60mL in 3h, the concentration of alum liquor is with Al
2O
3Count 200 g/L; Add simultaneously mass percent concentration and be 20% sodium hydroxide solution, keep slurry pH to 10, slaking 120min forms the first layer hydrated aluminum oxide coating layer on the TiO 2 particles surface;
5, continuation adding mass percent concentration is 20% sodium hydroxide solution, regulates the titania slurry pH value to 6 that coats hydrated aluminum oxide, slaking 120min;
6, will regulate titania slurry after the pH value with 80 ℃ deionized water washing, and filter, being washed till the filter cake specific conductivity is 20000 Ω cm;
7, in filter cake, add 4.0g Siloxane-Oxyalkylene Copolymers and 2.0g amino-long chain alkane comodified polysiloxane, under 2000rpm, carry out high speed dispersion 30min, so that form second layer silicone covering layer at the hydrated aluminum oxide coating layer, dry, gas powder is processed, and makes plastic color master grain tailored version TiO 2 pigment.
Embodiment 5
Component A phosphoric acid among component A Sodium hexametaphosphate 99 among the embodiment 1, the component A trisodium phosphate in the example 2, the component A trisodium phosphate among the embodiment 3 and tertiary sodium phosphate mixture, the embodiment 4 can be used at least a replacement in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid; Sodium metaaluminate among the embodiment 1 and potassium metaaluminate mixture can replace with sodium metaaluminate or potassium metaaluminate, sodium metaaluminate among the embodiment 2 can use at least a or potassium metaaluminate in sodium metaaluminate, the potassium metaaluminate to replace, aluminum chloride can use at least a or Tai-Ace S 150 in Tai-Ace S 150, the aluminum chloride to replace among the embodiment 3, and the Tai-Ace S 150 among the embodiment 4 can use at least a or aluminum chloride in Tai-Ace S 150, the aluminum chloride to replace.
Comparative Examples 1
Take by weighing alumina content and be 0.9%, D50 is the chlorination process rutile titanium dioxide first product powder 400g of 0.23 μ m, adds deionized water 800mL and is mixed with titania slurry, whole coating process is adopted pH meter test slurry pH value; Regulate titania slurry pH value to 7.0, slaking 90min with 20% sodium hydroxide solution; The slurry of slaking is washed with 70 ℃ deionized water, filter, being washed till the filter cake specific conductivity is 18000 Ω cm, in filter cake, add 0.8g Siloxane-Oxyalkylene Copolymers and 1.6g amino-long chain alkane comodified polysiloxane, under 1700rpm, carry out high speed dispersion 1.5h, make the TiO 2 particles surface form one deck silicone covering layer, dry, gas powder is processed, and makes the silicone covering TiO 2 pigment.
Comparative Examples 2
Take by weighing alumina content and be 0.9%, D50 is the chlorination process rutile titanium dioxide first product powder 400g of 0.23 μ m, adds deionized water 800mL and is mixed with titania slurry, whole coating process is adopted pH meter test slurry pH value; Regulate titania slurry pH value to 10.0 with sodium hydroxide solution, the 50g/L sodium hexametaphosphate solution 24mL(Vanadium Pentoxide in FLAKES of adding 0.3% accounts for titanium oxide gross weight meter), carry out sanded, sand milling disposed slurry D50 is that 350nm, D90 are 630nm, removes grinding medium from water slurry; The sand milling disposed slurry is warming up to 60 ℃, and adding concentration in the 1.0h is 150g/L sodium aluminate solution 53mL, and simultaneously, keeping slurry pH with 20% hydrochloric acid soln is 8.0, slaking 90min; Transfer endpoint pH to 7.0, slaking 90min; With the deionized water washing of slurry with 70 ℃, filter, being washed till the filter cake specific conductivity is 18000 Ω cm, and filtration cakes torrefaction, gas powder are processed, and makes the alumina-coated TiO 2 pigment.
With the TiO 2 pigment of embodiment 1～embodiment 4, Comparative Examples 1, Comparative Examples 2 preparations, the physical property of being correlated with and application performance test, detected result such as table 1:
Table 1
Remarks: the CR-510 product is the universal product of selling on the market for many years in the upper table; Photostabilization
Δ EDetection is the result at ultraviolet (UVA) light irradiation 10h; Thermotolerance
Δ EDetection is 240 ℃ of lower constant temperature 3h colour-change; Optical density value be will preparation the 60%PE white master batch to blow out titanium dioxide content be that 1% thickness is the 0.02mm film, pigment particles stops with light-absorbing ability stronger in the film, transmitted light intensity is just less, optical density value is just larger, the opacifying power of pigment is just higher in the film, and this moment, film looked just whiter and light tight; The dry powder flowability is the course of processing dry powder flow state of reflection product, directly affects charge weight stability, and numerical value is more low better; Melting index is mixture plasticizing rate speed, embodies the quality of the processing plasticizing performance of product; Dispersiveness is to adopt the particle size analysis method directly to measure the median size of blowing out particle in 1% film with 60% Masterbatch of titanium dioxide preparation.
As can be seen from Table 1: the outward appearance whiteness of the product that embodiment 1～embodiment 4 makes, dry powder flowability, thermotolerance, melting index and quite dispersed; Tinting strength, opacifying power and sunproof variation tendency are almost consistent, and this is relevant with titanium dioxide surface material and covering amount; The properties that considers indices embodiment 2 and embodiment 3 products is comparatively excellent;
The outward appearance whiteness of the product that embodiment 2, Comparative Examples 1, Comparative Examples 2 and CR-501 make is suitable; Comparative Examples 1 is not carried out alumina-coated, and photostabilization and the resistance toheat of product are very poor; Comparative Examples 2 is not carried out silicone covering, and processing plasticizing performance, melting index and the dispersing property of product are starkly lower than embodiment 2; CR-501 product whiteness, photostabilization and thermotolerance are slightly excellent, but tinting strength, opacifying power, melting index and dispersiveness obviously are worse than embodiment 2; The properties that considers indices embodiment 2 products is comparatively excellent;
In sum, the TiO 2 pigment of producing according to the present invention has excellent brightness, tinting strength, opacifying power, easily disperse, has good photostabilization, thermotolerance and processing plasticizing performance.
Claims (9)
1. the preparation method of a plastic color master grain tailored version TiO 2 pigment is characterized in that:
1.1, adopt chlorination process rutile titanium dioxide first product, add the titania slurry that a certain amount of deionized water is mixed with concentration 500g/L～800g/L, alumina content is 0.22 μ m～0.25 μ m at 0.6%～1.2%, D50 in the described titanium dioxide first product; Regulating titania slurry pH value with basic solution is 9.0～11.0, add component A, disperse 20min～30min, described component A is at least a in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid, wherein, Vanadium Pentoxide in FLAKES accounts for titanium dioxide first product weight and counts 0.1%～0.5% among the component A;
1.2, the titania slurry that disperses is carried out milled processed, and from water slurry, remove grinding medium;
1.3, the slurry after will grinding is heated to 50 ℃～80 ℃, and keeps this temperature in whole coating process;
1.4, in 0.5h～3h, add B component, described B component is acid aluminium salt compound or basic aluminium salt compound, described acid aluminium salt compound is at least a in Tai-Ace S 150, the aluminum chloride, described basic aluminium salt compound is at least a in sodium metaaluminate, the potassium metaaluminate, wherein, aluminum oxide accounts for titanium dioxide first product weight and counts 1.0%～3.0% in the B component; Simultaneously, by adding mineral acid or mineral alkali, keeping slurry pH is 5～10, and slaking 0.5h～2h forms the first layer hydrated aluminum oxide coating layer on the TiO 2 particles surface;
1.5, continue to add mineral acid or mineral alkali, regulating the titania slurry pH value that coats hydrated aluminum oxide is 6～8, slaking 1h～2h;
1.6, will regulate titania slurry after the pH value with 50 ℃～80 ℃ deionization washing, filter, be washed till filter cake specific conductivity＞15000 Ω cm;
1.7, add Siloxane-Oxyalkylene Copolymers and amino-long chain alkane comodified polysiloxane mixture in the filter cake, add-on counts 0.2%～1.5% with titanium dioxide first product weight, then under 1500rpm～2000 rpm, carry out high speed dispersion 30min～120min, so that form second layer silicone covering layer at the hydrated aluminum oxide coating layer, dry, gas powder is processed, and makes plastic color master grain tailored version TiO 2 pigment.
2. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1, it is characterized in that: the mass ratio of Siloxane-Oxyalkylene Copolymers and amino-long chain alkane comodified polysiloxane is 0.5:1～3:1 in the described mixture.
3. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1, it is characterized in that: the concentration of described component A solution is with P
2O
5Count 50g/L～200g/L.
4. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1, it is characterized in that: the concentration of described B component solution is with Al
2O
3Count 80 g/L～200g/L.
5. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1, it is characterized in that: after the milled processed, titania slurry particle diameter D50 is 300nm～400nm, D90＜700nm.
6. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1 is characterized in that: described component A is a kind of in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid.
7. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1, it is characterized in that: described component A is two kinds in Sodium hexametaphosphate 99, trisodium phosphate, tripoly phosphate sodium STPP, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, the phosphoric acid.
8. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1 is characterized in that: mineral acid described in step 1.4, the step 1.5 is at least a in hydrochloric acid, sulfuric acid, the nitric acid.
9. the preparation method of plastic color master grain tailored version TiO 2 pigment according to claim 1 is characterized in that: mineral alkali described in step 1.4, the step 1.5 is at least a in sodium hydroxide, the potassium hydroxide.
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| CN103627216B (en) * | 2013-11-08 | 2016-03-16 | 锦州钛业有限公司 | A kind of preparation method of special titanium dioxide pigment for electrophoretic paint |
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| CN104877393A (en) * | 2015-04-08 | 2015-09-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Titanium dioxide with low oil absorption and preparation method of titanium dioxide |
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| CN109111764A (en) * | 2018-08-30 | 2019-01-01 | 浙江天泰新材料科技有限公司 | Nano-powder titanium dioxide coating new material and preparation method thereof |
| CN109535775A (en) * | 2018-12-24 | 2019-03-29 | 攀钢集团重庆钛业有限公司 | The preparation method of ink tailored version titanium dioxide |
| CN109535775B (en) * | 2018-12-24 | 2020-11-24 | 攀钢集团重庆钛业有限公司 | Preparation method of titanium dioxide special for printing ink |
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| CN113698794A (en) * | 2021-08-25 | 2021-11-26 | 上海颜钛实业有限公司 | High-gloss high-weatherability titanium dioxide and preparation method thereof |
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