CN103224717A - Preparation method of composite coating titanium dioxide pigment - Google Patents
Preparation method of composite coating titanium dioxide pigment Download PDFInfo
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- CN103224717A CN103224717A CN2013100869718A CN201310086971A CN103224717A CN 103224717 A CN103224717 A CN 103224717A CN 2013100869718 A CN2013100869718 A CN 2013100869718A CN 201310086971 A CN201310086971 A CN 201310086971A CN 103224717 A CN103224717 A CN 103224717A
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Abstract
The invention discloses a preparation method of a composite coating titanium dioxide pigment. The preparation method comprises the following steps: simultaneously adding a common precipitating agent comprising a phosphoric water-soluble compound and an inorganic acid or inorganic base, and a water-soluble salt containing aluminum, zirconium, cerium, zinc, magnesium or tin to initial dispersed titanium dioxide, and coating the surface of the initial titanium dioxide with a layer of a mixed coat including a phosphate compound and an insoluble hydroxide. The pigment prepared through the method has the advantages of high light resistance, excellent covering power, and excellent oily whiteness, and can be used in coatings, plastics and papermaking.
Description
Technical field
The present invention relates to the field of TiO 2 pigment preparation, relate in particular to a kind of preparation method of TiO 2 pigment of composite coated raising light permanency.
Background technology
Advantages such as specific refractory power height, reducing power are strong because of having for titanium dioxide, glossiness and whiteness are good become best white pigment, are widely used in fields such as coating, plastics, papermaking, printing ink and chemical fibre.Yet since titanium dioxide particularly rutile titanium dioxide have photocatalytic activity, the organic composition that in use can catalyzed degradation contacts with it makes the matrix of contact with it produce phenomenons such as loss of gloss and powder of detached.In being used in decorative paper, decorative laminate is placed on when being exposed to the sun under daylight or the ultraviolet ray, photochemical reaction will take place in titanium dioxide, generate unsettled titanous (gloomy), because titanium dioxide is in the sealing anoxic environment, titanous can not react with airborne oxygen and be recovered to titanic in time.When the prolongation titanous along with the time of being exposed to the sun will be cumulative, therefore decorative laminate tarnishes the aged phenomenon will occur.Since the photocatalytic activity of titanium dioxide, the performance and the work-ing life of seriously reducing various products.
In order to suppress the photocatalytic activity of titanium dioxide, carry out the light permanency that particular processing is able to use on the surface of titanium dioxide usually.Known in this area at one or more layers silicon oxide of titanium dioxide granule surface-coated, aluminum oxide, the difficultly-soluble phosphates compound, sometimes also can be in coat the oxide compound of metals such as doped tin, cerium, vanadium.Those skilled in the art discover recently, more can improve the light permanency of TiO 2 pigment than independent cladded aluminium hydroxide, zirconium hydroxide etc. at the titanium dioxide surface coated phosphate.The oxyhydroxide of the indissoluble of molten phosphatic metal ion correspondence in distress generates simultaneously in the process of precipitate phosphoric acid salt.
Summary of the invention
The invention provides a kind of preparation method of composite coated TiO 2 pigment, the pigment that adopts this preparation method to make has very high light permanency.
A kind of preparation method of composite coated TiO 2 pigment comprises following step:
(1) the titanium dioxide first product is scattered in the aqeous suspension A that obtains the titanium dioxide first product in distilled water or the deionized water;
(2) will contain the water-soluble salt of first metal and first precipitation agent and join simultaneously among the aqeous suspension A that step (1) obtains and react, obtain aqeous suspension B;
Described first metal is aluminium, zirconium, cerium, zinc, magnesium or tin;
Described first metal is present in its water-soluble salt with the form of acid ion or metallic cation;
Described first precipitation agent is made up of components I and composition;
Described components I is the water-soluble cpds of phosphorus;
Described composition is mineral acid or mineral alkali;
(3) will contain the water-soluble salt of second metal and second precipitation agent and join simultaneously among the aqeous suspension B that step (2) obtains and react, obtain aqeous suspension C;
Described second metal is aluminium, zirconium, silicon, zinc or magnesium;
Described second metal is present in its water-soluble salt with the form of acid ion or metallic cation;
Described second precipitation agent is mineral acid or mineral alkali;
(4) pH value to 5～8 of the aqeous suspension C that obtains of regulating step (3) then after filtration, washing, drying and comminution by gas stream, obtain described composite coated TiO 2 pigment.
In the step of the present invention (2), contain the water-soluble salt of first metal and the phosphoric acid salt that the components I reaction generates insoluble, oxyhydroxide with composition reaction generation insoluble, phosphoric acid salt and oxyhydroxide generate simultaneously, surface precipitation at the titanium dioxide first product obtains one deck mixing coat, phosphorus and atoms metal have certain ratio in this mixing coat, and the mixing coat that obtains is fine and close more, thereby makes this pigment have higher light permanency.
Among the present invention, by changing the order of operation steps, the mixing coat that obtains can be at the innermost layer of the whole coat of titanium dioxide, middle layer or outermost layer.
As preferably, in the step (1), the preparation method of described aqeous suspension A is as follows:
(a) with distilled water or deionized water the titanium dioxide first product is made into slurry;
(b) add dispersion agent and the pH value transferred to 7～11 in the slurry in step (a), in sand mill, use screen filtration then behind the sand milling, obtain described aqeous suspension A.
In the step (a), described titanium dioxide first product can be the rutile titanium dioxide of producing by chlorination process, also can be rutile-type or the anatase titanium dioxide by Production By Sulfuric Acid Process, all can select the commercially available prod for use.As further preferred, described titanium dioxide first product is selected the titanium dioxide that has rutile-type structure basically for use.Concentration to titanium dioxide first product in the slurry does not have special requirement, and preferred, the concentration that contains the titanium dioxide first product in the slurry is 100g/L～500g/L.
In the step (b), described dispersion agent is one or both in water glass, the Sodium hexametaphosphate 99, and the mass ratio of described dispersion agent and titanium dioxide first product is 0.1～0.5:100.Water glass and Sodium hexametaphosphate 99 can adopt the mode of the aqueous solution to add, by adding above-mentioned dispersion agent, on the one hand because volume effect makes the titanium dioxide first product be evenly dispersed in the slurry system, on the other hand, owing to exist steric effect, make between the solid particulate because of electrostatic repulsion away from, thereby make solid particulate be difficult for agglomeration takes place, dispersion system is even, the particle suspension performance increases, thereby makes follow-up sand milling step have better effect.
In the step (b), by adding alkaline solution pH value of slurry is regulated, this alkaline solution is aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, ammonia soln or aqueous sodium carbonate.
In the step (2), the water-soluble salt that contains first metal can be the water soluble salt of aluminium, zirconium, cerium, zinc, magnesium or tin etc., and is concrete as Tai-Ace S 150, sodium metaaluminate, zirconium sulfate, cerous nitrate, zinc chloride or magnesium chloride etc.The add-on of these water-soluble salts is 0.5%～5% of a titanium dioxide first product add-on, and the add-on of water-soluble salt is in the quality of its maxivalence metal oxide, and the add-on of titanium dioxide first product is with TiO
2The quality meter.
In the step (2), described components I is the water-soluble cpds of phosphorus, specifically can select a kind of in alkali metal phosphate, ammonium phosphate, polyphosphate, the phosphoric acid etc. for use, and when first metal existed with the form of acid ion, components I was a phosphoric acid; When first metal existed with the form of metallic cation, components I was alkali metal phosphate, ammonium phosphate or polyphosphate.
The add-on of the water-soluble cpds of described phosphorus is 0.5%～5.0% of a titanium dioxide first product add-on, and the add-on of the water-soluble cpds of described phosphorus is with P
2O
5The quality meter, titanium dioxide first product add-on is with TiO
2The quality meter.
In the step (2), in water-soluble salt, when first metal existed with the form of acid ion, composition was a mineral acid; When first metal existed with the form of metallic cation, composition was a mineral alkali, and both neutralization reaction take place obtain precipitation of hydroxide, and the consumption of composition calculates based on basicity or acidity that can the neutral water-soluble salt.
As preferably, in the step (2), the described water-soluble salt that contains first metal is a sodium metaaluminate;
Described components I is a phosphoric acid;
Described composition is a sulfuric acid.At this moment, the lip-deep coat of the titanium dioxide first product among the aqeous suspension B is insoluble aluminum phosphate and alumag, the pigment light permanency height that finally obtains, and have good opacifying power, and the raw material that uses cheaply is easy to get.
As preferably, described phosphoric acid and vitriolic mole dosage are than being 1:0.1～5; As further preferred, described phosphoric acid and vitriolic mole dosage are than being 1:0.5～2, and at this moment, the ratio of phosphorus and its atoms metal keeps certain scope in the coat that obtains, and coat has higher compactness.
As other preferred, in the step (2), the described water-soluble salt that contains first metal is zirconium sulfate, cerous nitrate, magnesium chloride or zinc nitrate;
Described components I is Sodium phosphate dibasic or Sodium hexametaphosphate 99;
Described composition is sodium hydroxide or potassium hydroxide.At this moment, the lip-deep coat of the titanium dioxide first product among the aqeous suspension B is respectively insoluble zirconium phosphate and zirconium hydroxide mixture, Cerium monophosphate and cerous hydroxide mixture, trimagnesium phosphate and magnesium hydroxide mixture or zinc phosphate and zinc hydroxide mixture, the pigment light permanency height that finally obtains, and have good opacifying power, and the raw material that uses cheaply is easy to get.
As preferably, the mole dosage of described components I and composition is than being 1:0.1～5; As further preferred, the mole dosage of described components I and composition is than being 1:0.2～1.5, and the ratio of phosphorus and its atoms metal keeps certain scope in the coat that obtain this moment, and the compactness of coat is higher.
As preferably, in the step (2), contain the water-soluble salt of first metal and first precipitation agent adopts and the mode of stream adds, and keep pH constant during stream.
As further preferred, in the step (2), and to keep pH during stream be 2～11, is preferably 6～10, and can guarantee the smooth generation of oxyhydroxide this moment.
In the step (2), the too short throw out autohemagglutination that is easy to make generation of the joining day of water-soluble salt, rather than be formed uniformly the mixing coat of phosphoric acid salt and its oxyhydroxide, and the long production efficiency that can reduce of joining day has increased energy consumption simultaneously.So and the stream time be preferably 0.5h～5h, under this optimum condition, make on the surface of titanium dioxide coated phosphate and its oxyhydroxide mixing coat preferably.
In the step (3), the water-soluble salt and second precipitation agent that contain second metal react, and continue reaction, other compounds in the coating on the mixing coat surface that step (2) obtains, be preferably aluminium hydroxide, the concrete operations of this step are well known to those skilled in the art.
Wherein, described first metal and second metal can be metal of the same race or metal not of the same race.
The water-soluble salt that contains second metal can be Tai-Ace S 150, sodium metaaluminate, zirconium sulfate, zinc chloride or magnesium chloride.
Second precipitation agent can be sulfuric acid or sodium hydroxide.
The post-treating method of step (4) is well known to those skilled in the art, and the exsiccant temperature is preferably 100 ℃～300 ℃.
Compare with prior art, include the mixing coat of one deck densification in the pigment that preparation method of the present invention makes, wherein, the ratio of phosphorus and atoms metal can be controlled, have very high light permanency, and have good opacifying power and oiliness whiteness, can be used for coating, plastics and papermaking.
Description of drawings
Fig. 1 is the transmission electron microscope photo that embodiment 1 titanium dioxide surface has coated the mixing coat of aluminum phosphate and aluminium hydroxide;
Fig. 2 has coated the transmission electron microscope photo of the titanium dioxide granule of aluminum phosphate and part aluminium hydroxide (being to add sodium aluminate solution in the step 3) for Comparative Examples 1A titanium dioxide surface;
Fig. 3 is for adding the transmission electron microscope photo of the titanium dioxide granule behind the sodium aluminate solution in the Comparative Examples 1B step 3.
Embodiment
The performance test methods of the composite coated TiO 2 pigment that the present invention obtains is as follows: with TiO
2Pigment evenly spreads to and applies film forming in the resin, places irradiation certain hour under the light source, can judge TiO
2Light permanency.Concrete operating process is as follows, takes by weighing 1.20g TiO
2, join in the 6.0mL melamine resin, get finely dispersed mixed solution 2.0mL and evenly be coated on the slide glass, place it in 70 ℃ of oven dry in the loft drier.Take out, put into the Iodine gallium light printer and be exposed to the sun, the Iodine gallium light that to contain three power in the printer be 1000W, sample is 50cm apart from the vertical range of Iodine gallium light.Be exposed to the sun and take out behind the 2h, the aberration Δ E before and after test is exposed to the sun, E is more little for Δ, and light permanency is good more.
Embodiment 1
1) with deionized water with 1000g titanium dioxide first product (by the anatase titanium dioxide of Production By Sulfuric Acid Process, Ningbo Xinfu Titanium Dioxide Co., Ltd.), being mixed with the concentration that contains the titanium dioxide first product is the slurry of 320g/L, adding the Sodium hexametaphosphate 99 mass concentration is the sodium hexametaphosphate solution 0.05L of 70g/L, adding and containing the sodium hydroxide mass percent is that 20% aqueous sodium hydroxide solution is regulated pH to 8, then slurry is fed sand milling in the sand mill, slurry behind the sand milling obtains the aqeous suspension of titanium dioxide first product by screen cloth filtering coarse particles.
2) aqeous suspension with the titanium dioxide first product joins in the coating jar, stirs and be warming up to 40 ℃ simultaneously.
3) slowly add the sodium metaaluminate aqueous solution that concentration is 100g/L, add-on is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 4.0%; Add massfraction simultaneously and be 30% phosphoric acid solution and stream and keep pH=7～8, the add-on of phosphoric acid is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3.0%, contain sulfuric acid in the described phosphoric acid solution, phosphoric acid and vitriolic mol ratio are 1:0.5.
4) slowly adding the aluminum sulfate aqueous solution that concentration is 100g/L, is that 15% sulfuric acid and stream join in the reaction paste with mass percent, keeps pH=8.The add-on of the sodium metaaluminate aqueous solution is (with Al
2O
3The quality meter) be that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 2.0%.
5) treat that the sodium metaaluminate aqueous solution adds after, stir slaking 20min.With mass percent is that 15% sulfuric acid is regulated pH to 7, stirs slaking 40min, filters, uses deionized water wash, and drying obtains final pigment combination product through comminution by gas stream.
Be definite effect according to the inventive method, and the coating degree of co-precipitation aluminum phosphate aluminium hydroxide, we carry out the light permanency test to the final pigment of preparation.
Comparative Examples 1A
The used phosphoric acid of Comparative Examples 1A does not mix sulfuric acid, respectively with phosphoric acid and sulfuric acid priority and sodium aluminate solution and stream.Other step is identical with embodiment 1.
Comparative Examples 1B does not use phosphoric acid, and directly with sulfuric acid and sodium aluminate solution and stream, other step is identical with embodiment 1.
The test result such as the table 1 of the pigment light permanency of embodiment 1 and the preparation of its Comparative Examples:
Table 1
| Light permanency (aberration) | Embodiment 1 | Embodiment 1A | Embodiment 1B |
| △E | 2.1 | 3.8 | 6.6 |
The aberration minimum of embodiment 1 in the last table, the sun-proof performance is best, shows the aluminum phosphate of co-precipitation and the sun-proof performance that aluminium hydroxide can improve pigment.
Fig. 1 is the transmission electron microscope photo that embodiment 1 titanium dioxide surface has coated the mixing coat of aluminum phosphate and aluminium hydroxide;
Fig. 2 has coated the transmission electron microscope photo of the titanium dioxide granule of aluminum phosphate and part aluminium hydroxide (being to add sodium aluminate solution in the step 3) for Comparative Examples 1A titanium dioxide surface.
Fig. 3 is for adding the transmission electron microscope photo of the titanium dioxide granule behind the sodium aluminate solution in the Comparative Examples 1B step 3.
From photo as can be seen among the embodiment 1 the mixing coat of aluminum phosphate and aluminium hydroxide coat evenly fine and close, and Comparative Examples 1A does not adopt a lot of particles not of uniform size of the titanium dioxide granule surface precipitation that mixes coating, do not coat uniformly, Comparative Examples 1B has only precipitated aluminium hydroxide on the titanium dioxide granule surface, be adsorbed on the titanium dioxide granule surface as one deck tulle, do not have fine and close coating.Therefore adopt the coating method of patent of the present invention can prepare the coating layer of even compact, further improve the light permanency of pigment finished product.
Embodiment 2
With deionized water with 1000g titanium dioxide first product (by the rutile titanium dioxide of Production By Sulfuric Acid Process, Ningbo Xinfu Titanium Dioxide Co., Ltd.), be mixed with that to contain titanium dioxide first product concentration be the slurry of 280g/L, adding the water glass mass concentration is the sodium silicate aqueous solution 0.03L of 100g/L, adding and containing the sodium hydroxide mass percent is that 10% aqueous sodium hydroxide solution is regulated pH to 9, then slurry is fed sand milling in the sand mill, slurry behind the sand milling obtains the aqeous suspension of titanium dioxide first product by screen cloth filtering coarse particles.
The aqeous suspension of titanium dioxide first product is joined in the coating jar, stir and be warming up to 60 ℃ simultaneously.
Slowly adding concentration is the zirconium sulfate aqueous solution of 100g/L, and add-on is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 4.0%; Add massfraction simultaneously and be 30% disodium phosphate soln and stream and keep pH=2～2.5, the add-on of Sodium phosphate dibasic is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3.0%, the sodium hydroxide that contains in the described disodium phosphate soln, the content of sodium hydroxide based on can neutralisation of sulphuric acid acidity in the zirconium calculate.
Slowly adding concentration is the aluminum sulfate aqueous solution of 150g/L, is that 30% sodium hydroxide solution and stream join in the reaction paste with mass percent, keeps pH=2～2.5.The add-on of aluminum sulfate aqueous solution is (with Al
2O
3The quality meter) be that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3.0%.
After treating that aluminum sulfate aqueous solution adds, stir slaking 15min.With mass percent is that 30% aqueous sodium hydroxide solution is regulated pH to 7, stirs slaking 30min, filters, uses deionized water wash, and drying obtains final pigment combination product through comminution by gas stream.
Be definite effect according to the inventive method, and the co-precipitation zirconium phosphate, the coating degree of zirconium hydroxide, we carry out the light permanency test to the final pigment of preparation.
Comparative Examples 2A
The used Sodium phosphate dibasic of Comparative Examples 2A does not mix sodium hydroxide, respectively with Sodium phosphate dibasic and sodium hydroxide priority and zirconium sulfate solution and stream.Other step is identical with embodiment 2.
Comparative Examples 2B does not use Sodium phosphate dibasic, and directly with sodium hydroxide and zirconium sulfate solution and stream, other step is identical with embodiment 2.
The test result such as the following table of the pigment light permanency of embodiment 2 and the preparation of its Comparative Examples:
Table 2
| Light permanency (aberration) | Embodiment 2 | Embodiment 2A | Embodiment 2B |
| △E | 3.1 | 4.1 | 5.5 |
The aberration minimum of embodiment 2 in the last table, the sun-proof performance is best, shows the zirconium phosphate of co-precipitation and the sun-proof performance that zirconium hydroxide can improve pigment.
Embodiment 3
With deionized water with 1000g titanium dioxide first product (by the anatase titanium dioxide of Production By Sulfuric Acid Process, Ningbo Xinfu Titanium Dioxide Co., Ltd.), be mixed with that to contain titanium dioxide first product concentration be the slurry of 300g/L, adding the water glass mass concentration is the sodium silicate aqueous solution 0.03L of 100g/L, adding and containing the sodium hydroxide mass percent is that 10% aqueous sodium hydroxide solution is regulated pH to 10, then slurry is fed sand milling in the sand mill, slurry behind the sand milling obtains the aqeous suspension of titanium dioxide first product by screen cloth filtering coarse particles.
The aqeous suspension of titanium dioxide first product is joined in the coating jar, stir and be warming up to 70 ℃ simultaneously.
Slowly adding concentration is the cerous nitrate aqueous solution of 100g/L, and add-on is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 0.8%; Add massfraction simultaneously and be 25% sodium hexametaphosphate solution and stream and keep pH=10～10.5, the add-on of Sodium hexametaphosphate 99 is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 2.5%, contain sodium hydroxide in the described sodium hexametaphosphate solution, the content of sodium hydroxide based in the energy and cerous nitrate in acidity calculate.
Slowly adding concentration is the aluminum sulfate aqueous solution of 150g/L, is that 20% sulphuric acid soln and stream join in the reaction paste with mass percent, keeps pH=10～10.5.The add-on of the sodium metaaluminate aqueous solution is (with Al
2O
3The quality meter) be that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 5.0%.
After treating that the sodium metaaluminate aqueous solution adds, stir slaking 15min.With mass percent is that 20% sulphuric acid soln is regulated pH to 7, stirs slaking 30min, filters, uses deionized water wash, and drying obtains final pigment combination product through comminution by gas stream.
Be definite effect according to the inventive method, and the coating degree of co-precipitation Cerium monophosphate and cerous hydroxide, we carry out the light permanency test to the final pigment of preparation.
Comparative Examples 3A
The used Sodium hexametaphosphate 99 of Comparative Examples 3A does not mix sodium hydroxide, with using Sodium hexametaphosphate 99 and sodium hydroxide priority and cerous nitrate solution and stream respectively.Other step is identical with embodiment 3.
Comparative Examples 3B does not use Sodium hexametaphosphate 99, and directly with sodium hydroxide and cerous nitrate solution and stream, other step is identical with embodiment 3.
The test result such as the following table of the pigment light permanency of embodiment 3 and the preparation of its Comparative Examples:
Table 3
| Light permanency (aberration) | Embodiment 3 | Embodiment 3A | Embodiment 3B |
| △E | 2.8 | 3.6 | 4.3 |
The aberration minimum of embodiment 3 in the last table, the sun-proof performance is best, shows the Cerium monophosphate of co-precipitation and the sun-proof performance that cerous hydroxide can improve pigment.
Embodiment 4
With deionized water with 1000g titanium dioxide first product (rutile titanium dioxide of producing by chlorination process), be mixed with that to contain titanium dioxide first product concentration be the slurry of 320g/L, adding the Sodium hexametaphosphate 99 mass concentration is the sodium hexametaphosphate solution 0.05L of 70g/L, adding and containing the sodium hydroxide mass percent is that 30% aqueous sodium hydroxide solution is regulated pH to 8.5, then slurry is fed sand milling in the sand mill, slurry behind the sand milling obtains the aqeous suspension of titanium dioxide first product by screen cloth filtering coarse particles.
The aqeous suspension of titanium dioxide first product is joined in the coating jar, stir and be warming up to 60 ℃ simultaneously.
Slowly adding concentration is the magnesium chloride brine of 80g/L, and add-on is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 4%; Add massfraction simultaneously and be 35% disodium-hydrogen solution and stream and keep pH=8～9, the add-on of disodium-hydrogen is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3%, contain sodium hydroxide in the described disodium-hydrogen solution, the content of sodium hydroxide based in the energy and magnesium chloride in acidity calculate.
Slowly adding concentration is the aluminum sulfate aqueous solution of 150g/L, is that 20% sulphuric acid soln and stream join in the reaction paste with mass percent, keeps pH=8～9.The add-on of the sodium metaaluminate aqueous solution is (with Al
2O
3The quality meter) be that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 2.5%.
After treating that the sodium metaaluminate aqueous solution adds, stir slaking 15min.With mass percent is that 20% sulphuric acid soln is regulated pH to 7, stirs slaking 30min, filters, uses deionized water wash, and drying obtains final pigment combination product through comminution by gas stream.
Be definite effect according to the inventive method, and the trimagnesium phosphate that forms sediment altogether, the coating degree of magnesium hydroxide, we carry out the light permanency test to the final pigment of preparation.
Comparative Examples 4A
The used disodium-hydrogen of Comparative Examples 4A does not mix sodium hydroxide, with using disodium-hydrogen and sodium hydroxide priority and magnesium chloride solution and stream respectively.Other step is identical with embodiment 4.
Comparative Examples 4B does not use disodium-hydrogen, and directly with sodium hydroxide and magnesium chloride solution and stream, other step is identical with embodiment 4.
The test result such as the following table of the pigment light permanency of embodiment 4 and the preparation of its Comparative Examples:
Table 4
| Light permanency (aberration) | Embodiment 4 | Embodiment 4A | Embodiment 4B |
| △E | 3.0 | 3.9 | 4.7 |
The aberration minimum of embodiment 4 in the last table, the sun-proof performance is best, shows the trimagnesium phosphate of co-precipitation and the sun-proof performance that magnesium hydroxide can improve pigment.
Embodiment 5
With deionized water with 1000g titanium dioxide first product (rutile titanium dioxide of producing by chlorination process), be mixed with that to contain titanium dioxide first product concentration be the slurry of 320g/L, adding the Sodium hexametaphosphate 99 mass concentration is the sodium hexametaphosphate solution 0.05L of 70g/L, adding and containing the sodium hydroxide mass percent is that 30% aqueous sodium hydroxide solution is regulated pH to 8.5, then slurry is fed sand milling in the sand mill, slurry behind the sand milling obtains the aqeous suspension of titanium dioxide first product by screen cloth filtering coarse particles.
The aqeous suspension of titanium dioxide first product is joined in the coating jar, stir and be warming up to 80 ℃ simultaneously.
Slowly adding concentration is the zinc nitrate aqueous solution of 100g/L, and add-on is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3%; Add massfraction simultaneously and be 20% sodium hexametaphosphate solution and stream and keep pH=9～10, the add-on of Sodium hexametaphosphate 99 is that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3%, contain sodium hydroxide in the described sodium hexametaphosphate solution, the content of sodium hydroxide based in the energy and zinc nitrate in acidity calculate.
Slowly adding concentration is the aluminum sulfate aqueous solution of 110g/L, is that 15% sulphuric acid soln and stream join in the reaction paste with mass percent, keeps pH=9～10.The add-on of the sodium metaaluminate aqueous solution is (with Al
2O
3The quality meter) be that relative titanium dioxide first product add-on is (with TiO
2The quality meter) 3%.
After treating that the sodium metaaluminate aqueous solution adds, stir slaking 20min.With mass percent is that 20% sulphuric acid soln is regulated pH to 7, stirs slaking 30min, filters, uses deionized water wash, and drying obtains final pigment combination product through comminution by gas stream.
Be definite effect according to the inventive method, and the zinc phosphate that forms sediment altogether, the coating degree of zinc hydroxide, we carry out the light permanency test to the final pigment of preparation.
Comparative Examples 5A
The used Sodium hexametaphosphate 99 of Comparative Examples 5A does not mix sodium hydroxide, with using Sodium hexametaphosphate 99 and sodium hydroxide priority and zinc nitrate solution and stream respectively.Other step is identical with embodiment 5.
Comparative Examples 5B does not use Sodium hexametaphosphate 99, and directly with sodium hydroxide and zinc nitrate solution and stream, other step is identical with embodiment 5.
The test result such as the following table of the pigment light permanency of embodiment 5 and the preparation of its Comparative Examples:
Table 5
| Light permanency (aberration) | Embodiment 5 | Embodiment 5A | Embodiment 5B |
| △E | 2.4 | 3.7 | 5.0 |
The aberration minimum of embodiment 5 in the last table, the sun-proof performance is best, shows the zinc phosphate of co-precipitation and the sun-proof performance that zinc hydroxide can improve pigment.
Claims (8)
1. the preparation method of a composite coated TiO 2 pigment is characterized in that, comprises following step:
(1) the titanium dioxide first product is scattered in the aqeous suspension A that obtains the titanium dioxide first product in distilled water or the deionized water;
(2) will contain the water-soluble salt of first metal and first precipitation agent and join simultaneously among the aqeous suspension A that step (1) obtains and react, obtain aqeous suspension B;
Described first metal is aluminium, zirconium, cerium, zinc, magnesium or tin;
Described first metal is present in its water-soluble salt with the form of acid ion or metallic cation;
Described first precipitation agent is made up of components I and composition;
Described components I is the water-soluble cpds of phosphorus;
Described composition is mineral acid or mineral alkali;
(3) will contain the water-soluble salt of second metal and second precipitation agent and join simultaneously among the aqeous suspension B that step (2) obtains and react, obtain aqeous suspension C;
Described second metal is aluminium, zirconium, silicon, zinc or magnesium;
Described second metal is present in its water-soluble salt with the form of acid ion or metallic cation;
Described second precipitation agent is mineral acid or mineral alkali;
(4) pH value to 5～8 of the aqeous suspension C that obtains of regulating step (3) then after filtration, washing, drying and comminution by gas stream, obtain described composite coated TiO 2 pigment.
2. the preparation method of composite coated TiO 2 pigment according to claim 1 is characterized in that, in the step (2), the described water-soluble salt that contains first metal is a sodium metaaluminate;
Described components I is a phosphoric acid;
Described composition is a sulfuric acid.
3. the preparation method of composite coated TiO 2 pigment according to claim 2 is characterized in that, described phosphoric acid and vitriolic mole dosage are than being 1:0.1～5.
4. the preparation method of composite coated TiO 2 pigment according to claim 1 is characterized in that, in the step (2), the described water-soluble salt that contains first metal is zirconium sulfate, cerous nitrate, magnesium chloride or zinc nitrate;
Described components I is Sodium phosphate dibasic or Sodium hexametaphosphate 99;
Described composition is sodium hydroxide or potassium hydroxide.
5. the preparation method of composite coated TiO 2 pigment according to claim 4 is characterized in that, the mole dosage of described components I and composition is than being 1:0.1～5.
6. the preparation method of composite coated TiO 2 pigment according to claim 1 is characterized in that, in the step (2), contains the water-soluble salt of first metal and the mode of employing of first precipitation agent and stream and adds.
7. the preparation method of composite coated TiO 2 pigment according to claim 6 is characterized in that, in the step (2), and to keep pH be 2～11 when stream.
8. the preparation method of composite coated TiO 2 pigment according to claim 6 is characterized in that, and the stream time is 0.5～5h.
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| CN103436054A (en) * | 2013-08-29 | 2013-12-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Low viscosity enveloping method of titanium dioxide |
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