CN111334092A - Titanium dioxide for decorative paper and preparation method - Google Patents
Titanium dioxide for decorative paper and preparation method Download PDFInfo
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- CN111334092A CN111334092A CN202010288910.XA CN202010288910A CN111334092A CN 111334092 A CN111334092 A CN 111334092A CN 202010288910 A CN202010288910 A CN 202010288910A CN 111334092 A CN111334092 A CN 111334092A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- 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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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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Abstract
The invention discloses titanium dioxide for decorative paper and a preparation method thereof, wherein the titanium dioxide comprises a titanium dioxide substrate and an envelope layer positioned on the surface of the titanium dioxide substrate, and the envelope layer sequentially comprises a titanium phosphate and aluminum phosphate mixed envelope layer and a magnesium oxide and aluminum oxide mixed envelope layer from inside to outside. According to the titanium dioxide for the decorative paper, the titanium dioxide surface is coated with the titanium phosphate and aluminum phosphate mixed film layer, so that the hue of the titanium dioxide can be improved, the coating process of the titanium dioxide can be reduced, the cost is reduced, and then the titanium dioxide surface is coated with the aluminum oxide and magnesium oxide mixed film layer to improve the isoelectric point of the titanium dioxide, so that the titanium dioxide is positively charged in a paper making system, can be better combined with negatively charged cellulose, the retention rate of the titanium dioxide in paper is improved, and the covering power of the titanium dioxide is further improved. The invention takes the technical scheme as a starting point and also provides a preparation method of the titanium dioxide.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide, and particularly relates to titanium dioxide for decorative paper and a preparation method of the titanium dioxide.
Background
Titanium dioxide, also known as titanium dioxide, is considered to be the best white pigment in the world today due to its excellent optical properties, and is widely used in the fields of coatings, plastics, paper making, inks, chemical fibers and the like. In the field of papermaking, the decorative paper is the most titanium dioxide, and the using amount of titanium dioxide can reach 45%. Titanium dioxide for decorative paper should have good covering power, weather resistance (anti-powdering capability), color fastness and water dispersibility so as to ensure that the decorative paper has excellent use performance. However, some photoactivation points exist on the surface of titanium dioxide powder particles, and under the condition of moisture and by sunlight irradiation (mainly in a near ultraviolet spectrum region), oxygen ions on crystal lattices lose two electrons and are changed into oxygen atoms, and the nascent oxygen has extremely strong activity, so that organic substances in a coating film are oxidized, high molecular organic substances are subjected to chain scission and degradation, and the coating film is finally pulverized, lost of light, yellowed and discolored, so that the weather resistance is reduced. Therefore, the titanium dioxide pigments used in decorative papers have to be subjected to a special surface treatment.
Publication No. CN108929574A discloses a method for manufacturing titanium dioxide for decorative paper, wherein the inner layer is a cerium oxide film layer, then zirconium oxide is arranged, and the outermost layer is an aluminum oxide layer. Publication No. CN108587246A discloses a method for using chlorination by-product in titanium dioxide inorganic coating, which obtains titanium dioxide with light resistance close to that of cerium salt finished product, but the isoelectric point is lower, which results in lower papermaking retention.
Therefore, it is necessary to develop a new titanium pigment for decorative paper to solve the above technical problems.
Disclosure of Invention
The invention aims to provide titanium dioxide for decorative paper and a preparation method thereof to overcome the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
the titanium dioxide for the decorative paper comprises a titanium dioxide substrate and an envelope layer positioned on the surface of the titanium dioxide substrate, wherein the envelope layer sequentially comprises a titanium phosphate and aluminum phosphate mixed envelope layer and a magnesium oxide and aluminum oxide mixed envelope layer from inside to outside.
Preferably, the titanium phosphate and aluminum phosphate mixed coating layer is formed by adding phosphate, titanium salt and aluminum salt at the same time under the condition of pH 4.0-6.0 for reaction, wherein the adding amount of the phosphate is P2O5The mass of the titanium dioxide base material is 1.0-3.0%, and the addition amount of the titanium salt is TiO2The mass of the titanium dioxide base material is 0.1-1.0%; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 0.1-1.0%. Further preferably, the phosphate is Na2HPO4、Na3PO4、(NaPO3)6Or Na4P2O7At least one of (a); the titanium salt is titanyl dichloride and/or titanyl sulfate; the aluminum salt is sodium aluminate and/or potassium aluminate.
Preferably, the magnesium oxide and aluminum oxide mixed coating layer is formed by adding aluminum salt, magnesium salt and pH regulator at the same time under the condition of pH9.0-10.0, and the adding amount of the aluminum salt is Al2O3The mass of the titanium dioxide base material is 1-4%; the addition amount of the magnesium salt is 0.5-1.0% of the mass of the titanium dioxide base material by MgO. More preferably, the aluminum salt is Al2(SO4)3、AlCl3Or NaAlO2At least one of (a); the magnesium salt is MgSO4And/or MgCl2(ii) a The pH regulator is NaOH, KOH or H2SO4At least one of (1).
The preparation method of the titanium dioxide for the decorative paper comprises the following steps:
s1: preparing titanium dioxide-based material slurry, and heating to 60-90 ℃; simultaneously adding phosphate, titanium salt and aluminum salt into the slurry, controlling the pH to be 4.0-6.0, and then homogenizing; the phosphate additionAmount of P2O5Calculated by 0.5-3.0% of the mass of the titanium dioxide base material, the addition amount of the titanium salt is TiO2The mass of the titanium dioxide base material is 0.1-1.0%; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 0.1-1.0%;
s2: adjusting the pH value of the slurry to 9.0-10.0, and homogenizing; adding aluminum salt, magnesium salt and alkali into the slurry at the same time, keeping the pH value at 9.0-10.0, and then homogenizing; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 1-4%; the addition of the magnesium salt is 0.5-1.0% of the mass of the titanium dioxide base material by MgO;
s3: adjusting the pH value to 6.6-7.5, then homogenizing, and milling to obtain the titanium dioxide.
Preferably, in step S1, the phosphate, the titanium salt and the aluminum salt are added for 30-60 min, and the homogenization time is 20-30 min;
in the step S2, the pH adjusting time is 20-30 min, and the homogenizing time is 20-30 min; adding aluminum salt, magnesium salt and a pH regulator for 90-120 min, and homogenizing for 30-60 min;
in the step S3, the pH adjusting time is 30-60 min, and the homogenizing time is 90-120 min.
Preferably, in step S1, the phosphate is Na2HPO4、Na3PO4、(NaPO3)6Or Na4P2O7At least one of (a); the titanium salt is titanyl dichloride and/or titanyl sulfate; the aluminum salt is sodium aluminate and/or potassium aluminate.
Preferably, in step S2, the aluminum salt is Al2(SO4)3、AlCl3Or NaAlO2At least one of (a); the magnesium salt is MgSO4And/or MgCl2(ii) a The pH regulator is NaOH, KOH or H2SO4At least one of (1).
Preferably, the slurry concentration in step S1 is TiO2The amount is 250-800 g/L.
Preferably, step S3 further includes the steps of washing and flashing the slurry before milling.
According to the titanium dioxide for the decorative paper, the titanium dioxide surface is coated with the titanium phosphate and aluminum phosphate mixed film layer, so that the hue of the titanium dioxide can be improved, the coating process of the titanium dioxide can be reduced, the cost is reduced, and then the titanium dioxide surface is coated with the aluminum oxide and magnesium oxide mixed film layer to improve the isoelectric point of the titanium dioxide, so that the titanium dioxide is positively charged in a paper making system, can be better combined with negatively charged cellulose, the retention rate of the titanium dioxide in paper is improved, and the covering power of the titanium dioxide is further improved. The invention takes the technical scheme as a starting point and also provides a preparation method of the titanium dioxide.
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FIG. 1 is a Zeta potential performance test result chart of samples prepared in examples 1-3 and comparative example 2.
Detailed description of the preferred embodiments
The titanium dioxide for decorative paper provided by the invention comprises a titanium dioxide substrate and an envelope layer positioned on the surface of the titanium dioxide substrate, wherein the envelope layer sequentially comprises a titanium phosphate and aluminum phosphate mixed envelope layer and a magnesium oxide and aluminum oxide mixed envelope layer from inside to outside.
The traditional titanium dioxide for decorative paper needs to be coated with a layer of cerium phosphate on the surface of the titanium dioxide to improve the sun resistance of the titanium dioxide, but the addition of water-soluble cerium salt can cause the titanium dioxide to be in a yellowish phase; according to the titanium dioxide for the decorative paper, the color phase of the titanium dioxide can be improved by coating the titanium phosphate and aluminum phosphate mixed film layer on the surface of the titanium dioxide, and when the aluminum phosphate film layer is coated on the surface of the titanium dioxide, the prepared decorative laminated board is exposed to sunlight or ultraviolet rays, and TiO in the decorative layer is coated2Produce Ti3+In an oxygen-deficient environment, Ti3+Deprive PO4+The oxygen in the aluminum phosphate reduces the aluminum phosphate into aluminum phosphite, and the reaction formula is as follows:
Ti2O3+PO4 3-→2Ti O2+PO3 3-
since aluminum phosphite is white or transparent to TiO2Has little influence on whiteness, but produces muchPO of the amount3 3-When is PO3 3-Can be mixed with TiO2OH generated by photochemical reaction is combined to generate HPO4 2-The reaction formula is as follows:
PO3 3-+OH·→HPO4 2-
thereby preventing the chemically active OH from flowing into TiO2In the surrounding organic matrix, the organic matrix is prevented from being oxidized and degraded, and the light resistance of the titanium dioxide is improved. And the mixed coating can reduce the coating process of the titanium dioxide and reduce the cost. And then a layer of aluminum oxide and magnesium oxide mixed film is coated, because electrostatic attraction acts between the fibers and the titanium dioxide particles, the titanium dioxide particles are attached to the fibers, and the fibers are negatively charged, so that the titanium dioxide needs to be positively charged in a paper making system and can be better combined with negatively charged cellulose, the retention rate of the titanium dioxide in paper is improved, and the covering power of the titanium dioxide is further improved. And boehmite alumina hydrate AlOOH having an isoelectric point value of 9.4, Mg (OH)2The isoelectric point value is 12.4, therefore, magnesium oxide is coated to improve the isoelectric point of titanium dioxide, but in order to improve the dispersibility of the titanium dioxide, an alumina film layer is required to be coated on the outermost layer.
Preferably, the titanium phosphate and aluminum phosphate mixed coating layer is formed by adding phosphate, titanium salt and aluminum salt at the same time under the condition of pH 4.0-6.0 for reaction, wherein the adding amount of the phosphate is P2O5Calculated by the mass of the titanium dioxide base material, the titanium salt accounts for 1.0-3.0 percent of the mass of the titanium dioxide base material, and the addition amount of the titanium salt is TiO2The mass of the titanium dioxide base material is 0.1-1.0%; the amount of aluminum salt added is Al2O3The mass of the titanium dioxide base material is 0.1-1.0%; further preferably, the phosphate is Na2HPO4、Na3PO4、(NaPO3)6Or Na4P2O7The titanium salt can be selected from titanyl dichloride and/or titanyl sulfate; the aluminium salt can be sodium aluminate and/or potassium aluminate.
Preferably, the magnesium oxide and aluminum oxide mixed coating layer is formed by adding aluminum salt, magnesium salt and pH regulator at the same time under the condition of pH9.0-10.0, and the aluminum salt is added in an amount ofAl2O3The mass of the titanium dioxide base material is 1-4%; the addition amount of the magnesium salt is 0.5-1.0% of the mass of the titanium dioxide base material in terms of MgO. And a proper amount of coating agent is added to obtain a coating layer which is uniformly and completely covered.
Further preferably, the aluminum salt is Al2(SO4)3、AlCl3Or NaAlO2At least one of (a); the magnesium salt is MgSO4And/or MgCl2(ii) a The pH regulator can be NaOH, KOH, or H2SO4At least one of (1).
The preparation method of the titanium dioxide for the decorative paper comprises the following steps:
s1: preparing titanium dioxide-based material slurry, and heating to 60-90 ℃; simultaneously adding phosphate, titanium salt and aluminum salt into the slurry, controlling the pH to be 4.0-6.0, and then homogenizing; phosphate is added in an amount of P2O5Calculated by 1-3.0% of the mass of the titanium dioxide base material, the addition amount of the titanium salt is TiO2The mass of the titanium dioxide base material is 0.1-1.0%; the amount of aluminum salt added is Al2O3The mass of the titanium dioxide base material is 0.1-1.0%;
s2: adjusting the pH value of the slurry to 9.0-10.0, and homogenizing; adding aluminum salt, magnesium salt and alkali into the slurry at the same time, keeping the pH value at 9.0-10.0, and then homogenizing; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 1-4%; the addition of the magnesium salt is 0.5-1.0% of the mass of the titanium dioxide base material by MgO;
s3: adjusting the pH value to 6.6-7.5, then homogenizing, and milling to obtain the titanium dioxide.
The step S2 is carried out under alkaline condition, the obtained product is alkaline, and the performance of the titanium dioxide is easily affected under alkaline condition, so the step S3 adjusts the titanium dioxide to be neutral state, and the obtained titanium dioxide product has stable performance.
Research proves that the selection of proper slurry pH value and the addition amount of the coating agent play an important role in the formation of the film layer.
Preferably, in the step S1, the adding time of the phosphate, the titanium salt and the aluminum salt is 30-60 min, and the homogenizing time is 20-30 min;
s2pH, adjusting the time to be 20-30 min, and homogenizing the time to be 20-30 min; adding aluminum salt, magnesium salt and alkali for 90-120 min, and homogenizing for 30-60 min;
and S3pH, adjusting the time to be 30-60 min, and adjusting the homogenization time to be 90-120 min. The selection of proper adding time and homogenizing time of the coating agent also has important effects on the formation and stability of the film layer.
Preferably, the phosphate of step S1 is Na2HPO4、Na3PO4、(NaPO3)6Or Na4P2O7The titanium salt is titanyl dichloride and/or titanyl sulfate; the aluminium salt is sodium aluminate and/or potassium aluminate.
Preferably, the aluminum salt in step S2 is Al2(SO4)3、AlCl3Or NaAlO2At least one of (1), magnesium salt is MgSO4And/or MgCl2The pH regulator can be NaOH, KOH, or H2SO4At least one of (1).
Preferably, the phosphates, aluminium salts, etc. of steps S1 and S2 are added in the form of a solution, in particular a phosphate solution of step S1, in the form of P2O5The concentration is 80-100 g/L, and the titanium salt solution is TiO2The solution concentration is 100-140 g/L, and the aluminum salt solution is Al2O3The concentration is 80-200 g/L; step S2 aluminum salt solution with Al2O3The concentration is 80-200 g/L; the magnesium salt solution has a concentration of 80-200 g/L in terms of MgO.
Preferably, the slurry concentration of step S1 is TiO2The amount is 250-800 g/L.
Preferably, step S3 further includes the steps of washing and flashing the slurry before milling.
Example 1
The sand grinding slurry is led into a coating tank, and the concentration of the slurry is controlled to be 350g/L (by TiO)2Metering), and simultaneously heating to 80 ℃; na accounting for 2.8 percent of the mass fraction of the titanium dioxide in the slurry is added within 60min4P2O7Solution, 0.8% TiOCl2Homogenizing the solution and 0.6% sodium aluminate solution for 30min by controlling the pH value to be 4.5-5.5; adjusting the pH value of the slurry to 9.5 with dilute NaOH solution, adjusting for 30min, and homogenizing for 30 min; NaAlO accounting for 2.5 percent of the mass fraction of the titanium dioxide in the slurry is added within 120min2Solution, 1.0% MgSO4Solution and H2SO4Maintaining the pH of the solution at 9.5 and homogenizing for 30 min; with dilute H2SO4Adjusting pH to 7.0, adjusting for 30min, and homogenizing for 120 min; washing, flash evaporation and steam powder to obtain the product.
Example 2
The sand grinding slurry is led into a coating tank, and the concentration of the slurry is controlled to be 350g/L (by TiO)2Metering), and simultaneously heating to 80 ℃; na accounting for 2.0 percent of the mass fraction of the titanium dioxide in the slurry is added within 60min4P2O7Solution, 0.6% TiOCl2Homogenizing the solution and 0.4% sodium aluminate solution for 30min by controlling the pH value to be 4.5-5.5; adjusting the pH value of the slurry to 9.5 with dilute NaOH solution, adjusting for 30min, and homogenizing for 30 min; NaAlO accounting for 3.0 percent of the mass fraction of the titanium dioxide in the slurry is added within 100min2Solution, 0.8% MgSO4Solution and H2SO4Maintaining the pH of the solution at 9.5 and homogenizing for 30 min; with dilute H2SO4Adjusting pH to 7.0, adjusting for 30min, and homogenizing for 120 min; washing, flash evaporation and steam powdering to obtain the product, and the rest is the same as the example 1.
Example 3
The sand grinding slurry is led into a coating tank, and the concentration of the slurry is controlled to be 350g/L (by TiO)2Metering), and simultaneously heating to 80 ℃; na accounting for 1.2 percent of the mass fraction of the titanium dioxide in the slurry is added within 60min2HPO4Solution (with P)2O5The solution concentration is 90g/L), 0.4 percent of TiOCl2Solution (in TiO)2120g/L solution concentration) and 0.23% sodium aluminate solution (in terms of Al)2O3Measuring the solution concentration to be 140g/L), controlling the pH to be 4.5-5.5, and homogenizing for 30 min; adjusting pH of the slurry to 9.5 with dilute NaOH solution (solution concentration 240g/L), adjusting for 30min, and homogenizing for 30 min; NaAlO accounting for 3.5 percent of the mass fraction of the titanium dioxide in the slurry is added within 90min2Solution (with Al)2O3Metering and dissolvingLiquid concentration 140g/L), 0.5% MgSO4Solution (solution concentration 140g/L as MgO) and dilute H2SO4Homogenizing the solution (solution concentration 240g/L) for 30min while keeping the pH of the solution at 9.5; with dilute H2SO4Adjusting pH to 7.0 (concentration of solution 130g/L), adjusting for 30min, and homogenizing for 120 min; washing, flash evaporation and steam powder to obtain the product.
Comparative example 1. coating with Ce, Zr and Al
The sand grinding slurry is led into a coating tank, and the concentration of the slurry is controlled to be 300g/L (by TiO)2Metering), and simultaneously heating to 40 ℃; adding Ce (SO) accounting for 0.4 percent of the mass fraction of the titanium dioxide (calculated by cerium oxide) in the slurry within 30min4)2Stirring the solution (the solution concentration is 90g/L) and 0.4% trimethylolethane for 30 min; h2SO4(the solution concentration is 130g/L) to adjust the pH value to 2.0, and Zr (SO) accounting for 0.4 percent of the mass fraction of the titanium dioxide in the slurry is added within 30min4)2Homogenizing the solution (the concentration of the solution is 90g/L in terms of zirconia) for 2 hours; adjusting the pH value of NaOH solution (240 g/L) to 9.0, and homogenizing for 30 min; NaAlO accounting for 4.5 percent of the mass fraction of the titanium dioxide in the slurry is added within 30min2Solution (with Al)2O3% solution concentration 140g/L), homogenizing for 30min with H2SO4Adjusting pH of the solution (130g/L) to 6.0, adjusting for 90min, and homogenizing for 30 min; filtering and washing the filter cake, drying and pulverizing to obtain the finished product.
Comparative example 2 composite coating of titanium, phosphorus and aluminum
The sand grinding slurry is led into a coating tank, and the concentration of the slurry is controlled to be 300g/L (by TiO)2Metering), and simultaneously heating to 40 ℃; TiCl accounting for 0.15 percent of the mass fraction of the titanium dioxide in the slurry is added within 40min4(in the form of TiO)2Calculated), while adding 1.0% Na2HPO4Solution and 2.0% Na3PO4Solution (with P)2O5Measuring the concentration of the solution to be 90g/L), and homogenizing for 60 min; heating to 80 deg.C, and adding NaAlO2(the concentration is 140g/L) adjusting the pH value to be 6.8-7.0, and adding H accounting for 1.0 percent of the mass fraction of the titanium dioxide in the slurry within 90min3PO4(with P)2O5Calculated by 110g/L) and NaAlO2Parallel flow, keeping pH value at 6.8-7.0, homogenizing 45min; adding 4% NaAlO within 120min2Solution (with Al)2O3% solution concentration 140g/L) and dilute H2SO4Homogenizing the solution (the concentration of the solution is 130g/L) for 30min while keeping the pH value of the solution in parallel flow to be 6.8-7.0; with dilute H2SO4Adjusting the pH value to 5.3-5.5 (the solution concentration is 130g/L), adjusting for 30min, and homogenizing for 120 min; washing, flash evaporation and steam powder to obtain the product.
Comparison of the results of the examples and comparative examples
1. Zeta potential
The Zeta potential performance tests were performed on the samples prepared in examples 1 to 3 and comparative example 2, and the results are shown in table 1 and fig. 1.
TABLE 1
| Sample (I) | Isoelectric point |
| Comparative example 2 | 5.9 |
| Example 1 | 7.1 |
| Example 2 | 6.8 |
| Example 3 | 6.7 |
As can be seen from the data in Table 1 and FIG. 1, in the examples 1-3, compared with the comparative example, the zeta potential is improved, and the retention rate of the titanium dioxide in the paper can be improved.
2. Comparison of application Properties (example vs. comparative papermaking)
Samples prepared in examples 1-3 and comparative examples 1-2 were taken for application performance testing, and the results are shown in table 2.
TABLE 2
As can be seen from the data in Table 2, the covering power, the lightness L, the red-green index L and the Ganz whiteness Wg of the titanium dioxide prepared in the examples 1 to 3 are all larger than those of the comparative example, and the light resistance delta E and the yellow-blue index b are all smaller than those of the comparative example, which shows that the titanium dioxide prepared by the method has higher hue and higher covering power in papermaking, and the light resistance is basically equivalent to that of the comparative example.
While preferred embodiments of the present invention 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. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The titanium dioxide for the decorative paper is characterized by comprising a titanium dioxide substrate and an envelope layer positioned on the surface of the titanium dioxide substrate, wherein the envelope layer sequentially comprises a titanium phosphate and aluminum phosphate mixed envelope layer and a magnesium oxide and aluminum oxide mixed envelope layer from inside to outside.
2. A titanium dioxide powder for decorative paper according to claim 1, wherein,
the titanium phosphate and aluminum phosphate mixed coating layer is formed by adding phosphate, titanium salt and aluminum salt at the same time under the condition of pH4.0-6.0 for reaction, wherein the adding amount of the phosphate is P2O5Measured as the titanium dioxide base1.0-3.0% of the material by mass, wherein the addition amount of the titanium salt is TiO2The mass of the titanium dioxide base material is 0.1-1.0%; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 0.1-1.0%.
3. A titanium dioxide powder for decorative paper according to claim 1, wherein,
the magnesium oxide and aluminum oxide mixed coating layer is formed by simultaneously adding aluminum salt, magnesium salt and a pH regulator under the condition of pH9.0-10.0, wherein the addition amount of the aluminum salt is Al2O3The mass of the titanium dioxide base material is 1-4%; the addition amount of the magnesium salt is 0.5-1.0% of the mass of the titanium dioxide base material by MgO.
4. A titanium dioxide powder for decorative paper according to claim 2, wherein,
the phosphate is Na2HPO4、Na3PO4、(NaPO3)6Or Na4P2O7At least one of (a); the titanium salt is titanyl dichloride and/or titanyl sulfate; the aluminum salt is sodium aluminate and/or potassium aluminate.
5. A titanium dioxide powder for decorative paper according to claim 3, wherein,
the aluminum salt is Al2(SO4)3、AlCl3Or NaAlO2At least one of (a); the magnesium salt is MgSO4And/or MgCl2(ii) a The pH regulator is NaOH, KOH or H2SO4At least one of (1).
6. A preparation method of titanium dioxide for decorative paper according to any one of claims 1 to 5, characterized by comprising the following steps:
s1: preparing titanium dioxide-based material slurry, and heating to 60-90 ℃; simultaneously adding phosphate, titanium salt and aluminum salt into the slurry, controlling the pH to be 4.0-6.0, and then homogenizing; the phosphate saltAdded in an amount of P2O5Calculated by 0.5-3.0% of the mass of the titanium dioxide base material, the addition amount of the titanium salt is TiO2The mass of the titanium dioxide base material is 0.1-1.0%; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 0.1-1.0%;
s2: adjusting the pH value of the slurry to 9.0-10.0, and homogenizing; adding aluminum salt, magnesium salt and alkali into the slurry at the same time, keeping the pH value at 9.0-10.0, and then homogenizing; the aluminum salt is added in an amount of Al2O3The mass of the titanium dioxide base material is 1-4%; the addition of the magnesium salt is 0.5-1.0% of the mass of the titanium dioxide base material by MgO;
s3: adjusting the pH value to 6.6-7.5, then homogenizing, and milling to obtain the titanium dioxide.
7. A process for the preparation of titanium dioxide for decorative paper according to claim 6, wherein,
in the step S1, the adding time of the phosphate, the titanium salt and the aluminum salt is 30-60 min, and the homogenizing time is 20-30 min;
in the step S2, the pH adjusting time is 20-30 min, and the homogenizing time is 20-30 min; adding aluminum salt, magnesium salt and a pH regulator for 90-120 min, and homogenizing for 30-60 min;
in the step S3, the pH adjusting time is 30-60 min, and the homogenizing time is 90-120 min.
8. A process for the preparation of titanium dioxide for decorative paper according to claim 6, wherein,
in step S1, the phosphate is Na2HPO4、Na3PO4、(NaPO3)6Or Na4P2O7At least one of (a); the titanium salt is titanyl dichloride and/or titanyl sulfate; the aluminum salt is sodium aluminate and/or potassium aluminate.
9. A process for the preparation of titanium dioxide for decorative paper according to claim 6, wherein,
in step S2, the aluminum salt is Al2(SO4)3、AlCl3Or NaAlO2At least one of (a); the magnesium salt is MgSO4And/or MgCl2(ii) a The pH regulator is NaOH, KOH or H2SO4At least one of (1).
10. A process for the preparation of titanium dioxide for decorative paper according to claim 6, wherein,
in step S1, the slurry concentration is TiO2The amount is 250-800 g/L.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112175420A (en) * | 2020-10-09 | 2021-01-05 | 安徽金星钛白（集团）有限公司 | Rutile type titanium dioxide crude product with high light resistance and preparation method and application thereof |
| CN113185853A (en) * | 2021-04-23 | 2021-07-30 | 河南佰利联新材料有限公司 | Preparation method of titanium dioxide for antibacterial coating |
| CN113773672A (en) * | 2021-09-30 | 2021-12-10 | 福建坤彩材料科技股份有限公司 | White pearlescent pigment and preparation method and application thereof |
| CN113914131A (en) * | 2021-10-19 | 2022-01-11 | 龙佰集团股份有限公司 | Method for improving retention rate of papermaking titanium dioxide |
| CN114031956A (en) * | 2021-12-01 | 2022-02-11 | 龙佰集团股份有限公司 | Preparation method of titanium dioxide with high light resistance and low cost |
| CN115678316A (en) * | 2022-10-26 | 2023-02-03 | 徐州钛白化工有限责任公司 | Preparation method of special titanium dioxide slurry for papermaking |
| CN116356602A (en) * | 2023-03-17 | 2023-06-30 | 河南佰利联新材料有限公司 | Recyclable switch-type titanium dioxide special for papermaking and preparation method thereof |
| CN116445010A (en) * | 2023-04-20 | 2023-07-18 | 龙佰集团股份有限公司 | Coating-used recoated titanium dioxide and preparation method thereof |
| CN116554767A (en) * | 2023-03-28 | 2023-08-08 | 江苏镇钛化工有限公司 | Titanium dioxide for coating based on high temperature resistance and preparation process thereof |
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| CN112175420A (en) * | 2020-10-09 | 2021-01-05 | 安徽金星钛白（集团）有限公司 | Rutile type titanium dioxide crude product with high light resistance and preparation method and application thereof |
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| CN113185853B (en) * | 2021-04-23 | 2021-11-12 | 河南佰利联新材料有限公司 | Preparation method of titanium dioxide for antibacterial coating |
| CN113773672A (en) * | 2021-09-30 | 2021-12-10 | 福建坤彩材料科技股份有限公司 | White pearlescent pigment and preparation method and application thereof |
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| CN114031956A (en) * | 2021-12-01 | 2022-02-11 | 龙佰集团股份有限公司 | Preparation method of titanium dioxide with high light resistance and low cost |
| CN115678316A (en) * | 2022-10-26 | 2023-02-03 | 徐州钛白化工有限责任公司 | Preparation method of special titanium dioxide slurry for papermaking |
| CN116356602A (en) * | 2023-03-17 | 2023-06-30 | 河南佰利联新材料有限公司 | Recyclable switch-type titanium dioxide special for papermaking and preparation method thereof |
| CN116356602B (en) * | 2023-03-17 | 2024-04-02 | 河南佰利联新材料有限公司 | Recyclable switch-type titanium dioxide special for papermaking and preparation method thereof |
| CN116554767A (en) * | 2023-03-28 | 2023-08-08 | 江苏镇钛化工有限公司 | Titanium dioxide for coating based on high temperature resistance and preparation process thereof |
| CN116445010A (en) * | 2023-04-20 | 2023-07-18 | 龙佰集团股份有限公司 | Coating-used recoated titanium dioxide and preparation method thereof |
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