CN102675928A - Rutile-type synthetic mica pearlescent pigment and preparation method thereof - Google Patents

Rutile-type synthetic mica pearlescent pigment and preparation method thereof Download PDF

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CN102675928A
CN102675928A CN2012101599887A CN201210159988A CN102675928A CN 102675928 A CN102675928 A CN 102675928A CN 2012101599887 A CN2012101599887 A CN 2012101599887A CN 201210159988 A CN201210159988 A CN 201210159988A CN 102675928 A CN102675928 A CN 102675928A
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solution
rutile
mica
synthetic mica
solubility
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CN102675928B (en
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杨伦全
谢秉昆
吴跃金
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FUJIAN KUNCAI MATERIAL TECHNOLOGY CO., LTD.
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FUZHOU KUNCAI FINE CHEMICALS LLC
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Abstract

The invention relates to a rutile-type synthetic mica pearlescent pigment and a preparation method thereof. The preparation method comprises the following steps: by using synthetic mica as a substrate, reducing Ti<4+> in part of soluble titanic (Ti4<+>) salt into Ti<3+> with an aluminum sheet; carrying out hydrolysis coating with the Ti<3+>, wherein the Ti<3+> hydrolyzate is used as a crystallization inducer, and the TiO2 amount formed by hydrolysis deposition of the soluble titanic salt is 1-6 wt% of the synthetic mica, preferably 2-5 wt%; continuing the hydrolysis deposition coating on the rest soluble titanic (Ti4<+>) salt solution, wherein the amount of the rest soluble titanic salt enables the total TiO2 coating rate to be generally 5-60%; and calcining to obtain the rutile-type synthetic mica pearlescent pigment. The rutile-type synthetic mica pearlescent pigment is free of SnO2, has the advantages of high whiteness (silver white series) and bright color (irisation series and metallic color series), and can be widely used in cosmetics, plastics, synthetic leather, ink, wallpaper, paint and other industries.

Description

A kind of rutile-type synthetic mica pearly pigment and preparation method thereof
Technical field
The present invention relates to a kind of rutile-type synthetic mica pearly pigment and preparation method thereof, belong to inorganic non-metallic effect pigment field.
Background technology
Common a kind of pearly pigment is to be base material with transparent flaky material, hydrolysis solubility titanium salt, and deposition of titanium oxide coating layer and the pearly pigment that obtains, it is a kind of interference of light effect pigment, presents different pigment along with the difference of coating layer thickness.Titanium oxide as coating has three kinds of crystalline structures: plate titanium type, anatase titanium dioxide, rutile-type.Plate titanium type is a kind of metastable-state crystal, can in coating layer, not occur.Titanium salt hydrolysis deposition is that the form with metatitanic acid is deposited on substrate surface, after the high-temperature calcination dehydration, at first generates anatase titanium dioxide TiO 2, under long-time high temperature or lead in the presence of the brilliant agent and be converted into rutile TiO 2Rutile-type has structure more closely than anatase titanium dioxide, thereby higher specific refractory power (anatase titanium dioxide TiO is arranged 2Specific refractory power is 2.52, rutile TiO 2Specific refractory power is 2.72), better chemicalstability, temperature tolerance, weathering resistance have more excellent quality, purposes widely.
With the synthetic mica is base material; With the solubility titanium salt is presoma; Hydrolysis deposition cladding titanium dioxide and to obtain a kind of synthetic mica pearly pigment be proven technique comparatively, its coating layer of the pearly pigment that obtains by this way is the titanium oxide of anatase titanium dioxide, although anatase titanium dioxide progressively is converted into rutile titanium dioxide through long-time high-temperature calcination meeting; But conversion process slowly and not exclusively, and higher invert point will be arranged.As above-mentioned, the rutile-type pearly pigment has higher gloss, better weather resistance, and in order to obtain the golden red type pearly pigment of better quality, common way is to be coated with before the titanium dioxide layer, to coat one deck tindioxide and lead brilliant agent, Sn is being arranged 4+Lead brilliant agent and exist down, the anatase titanium dioxide layer can be converted into the red schorl type titanium dioxide coating layer quickly in lower temperature range, thereby obtains a kind of rutile-type pearly pigment.But American-European have strict restriction, pearly pigment SnO at cosmetic industry to the use of Sn 2Therefore content must be used for the product of eye less than 0.5%, can not contain, and must find a kind ofly can prepare the rutile-type pearly pigment and don't use Sn 4+As the method for leading brilliant agent.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of rutile-type synthetic mica pearly pigment and preparation method thereof is provided.
According to first aspect, the present invention relates to a kind of rutile-type synthetic mica pearly pigment, it be through with aluminium flake with a part of solubility titanic (Ti 4+) Ti of salts solution 4+Ion is reduced into Ti 3+Ion and obtain to contain Ti 3+Ion solution is added the above-mentioned Ti of containing then in the slurry material that is formed by synthetic mica and water as base material (pH that preferably regulates it with hydrochloric acid is in 1.6 ~ 2.2 scopes) 3+Ion solution at first be hydrolyzed (preferred, when adding through adding pH that alkali keeps this system) in 1.6 ~ 2.2 scopes realize preliminary coating, wherein this part solubility titanic (Ti for the weight of synthetic mica 4+) consumption of salts solution should make by Ti 3+The sedimentary TiO of hydrolysis 2Amount for synthetic mica weight 1 ~ 6%, preferred 2 ~ 5%, and then add the solubility titanic (Ti of remainder 4+) salts solution proceeds hydrolysis deposition and further implement coating, wherein the solubility titanic (Ti of this remainder 4+) consumption of salt should make based on total TiO of base material weight 2Clad ratio is 5 ~ 60% (preferred 6 ~ 50%, more preferably 7 ~ 45%, further preferred 8 ~ 40%), calcines then and finally obtains.Described here " contains Ti 3+Solution " also can be called for short " Ti in this application 3+Solution ".Described in this application in addition " tetravalent salt of titanium solution ", " Ti 4+Salts solution ", " Ti 4+Solution " and " contain Ti 4+Solution " interchangeable each other use, promptly they are identical notions.
Ti 3+Be a kind of good anatase titanium dioxide TiO 2Be converted into rutile TiO 2Lead brilliant agent.Ti 3+With Ti 4+Be similar different valency material, Ti 3+The TiO that hydrolysis generates 2Crystal has defective, and this just lattice defect can quicken anatase titanium dioxide TiO 2To rutile TiO 2Conversion, and with Ti 3+As the great advantage of leading brilliant agent is can not introduce other material, obtains a kind of fully by TiO 2The pearly pigment of coating.
Ti 3+Solution is extremely unstable, behind ingress of air, can be oxidized to Ti very soon 4+Solution, and lose the effect of leading brilliant agent.So Ti 3+Solution is wanted now-making-now-using.
Preferably, the solubility tetravalent salt of titanium is selected from TiCl 4, TiOSO 4Deng in one or more.
Preferably; Said aluminium flake is that purity is greater than 99.5%; The aluminium flake of thickness 0.1 ~ 1mm (to the not special restriction of the length and width size of aluminium flake), its addition (by quality or weight) are to make Restore All on the Ti4+ ionic theory of said a part of solubility tetravalent salt of titanium become 3 ~ 5 times amount of that Theoretical Calculation aluminium flake consumption (by quality or weight) of Ti3+ ionic.
According to second aspect, the present invention relates to the preparation method of rutile-type synthetic mica pearly pigment, it is characterized in that comprising:
(1) gets the solubility titanic (T of 0.5 ~ 4.5mol/L concentration 4+) hydrochloric acid (v/v) 1:2 ~ 5 by volume of salts solution and 1 ~ 5mol/L concentration, preferred 1:3 mixes and obtains>=obtain solution of V (L) volume;
(2) get the above-mentioned obtain solution of V (L) volume in the middle of the obtain solution that obtains from step (1), wherein volume V confirms according to following formula:
V=0.0125PW Mica(1+A)/(AC Ti)
P: in following steps (5) by containing Ti 3+Solution water separate the formed TiO of coating 2The per-cent of weight and compound mica weight; General P=1 ~ 6%, preferred P=2 ~ 5%;
W Mica: the consumption of compound mica, g;
A: solubility titanic (Ti 4+) volume ratio of salts solution and hydrochloric acid soln, be generally 1:2 ~ 5, preferred 1:3;
C Ti: solubility titanic (Ti 4+) volumetric molar concentration of salts solution, be generally 0.5 ~ 4.5mol/L;
(3) calculate according to following formula, add W in the solution of V (L) volume of in step (2), being got AlAluminium flake, the reaction to there not being bubble, promptly obtain the Ti that contains of lilac 3+Solution;
W Al=9KVAC Ti/（1+A）
W Al: need be with the amount of aluminium flake, g;
V: need reductive Ti 4+The volume number of salts solution, L;
K: excess coefficient, wherein K=3 ~ 5, preferably K=4;
A:Ti 4+The volume ratio of salts solution and hydrochloric acid soln is generally 1:2 ~ 5, preferred 1:3;
C Ti: Ti 4+The volumetric molar concentration of salts solution is generally 0.5 ~ 4.5mol/L;
(4) get some amount (W MicaGram) pearly-lustre level compound mica and water; Preferred specific conductivity is less than the reverse osmosis water of 20 μ s/cm or the specific conductivity deionized water less than 50 μ s/cm; Be made into the slurry material by solid-to-liquid ratio 1:6 ~ 12 stirrings; Under whipped state, the slurry material is warming up to 65 ~ 85 ℃, regulating the pH value with Hydrogen chloride (for example 1M concentration) is 1.6 ~ 2.2;
(5) in the slurry material that above step (4) is obtained, drip the Ti that contains of step (3) gained 3+Solution, wherein rate of addition be the per kilogram compound mica per hour 0.5～1.25L contain Ti 3+Solution, use pH value stabilization that alkali (alkali lye for example, like NaOH solution, KOH solution, ammonia soln, especially the NaOH solution of 10 ~ 30wt% concentration, more specifically 20% concentration NaOH solution) keeps system 1.6 ~ 2.2, up to containing Ti simultaneously 3+Solution addition till;
(6) keep continuing to drip the Ti of 0.5 ~ 4.5mol/L concentration under uniform temp, the identical pH condition 4+Salts solution, wherein rate of addition per hour drips the Ti of 0.25 ~ 0.75mol by the per kilogram compound mica 4+Come to confirm, be dosed to required form and aspect (for example silvery white standard form and aspect) always after, stopping to feed in raw material (generally needs to add 0.625 ~ 7.5mol Ti 4+/ kg compound mica), continue constant temperature then and stir 10 ~ 30min;
(7) with step (6) gained slurries filtration; Washing to pH=5 ~ 7 with reverse osmosis water, is dry (for example 2 h ~ are 24 hours, preferred 6 ~ 12 hours) under 100 ~ 150 ℃ of (preferred 120～140 ℃) conditions in temperature; 500 ~ 900 ℃ (preferred 600 ~ 850 ℃; More preferably 650 ~ 800 ℃) calcining (for example 20 minutes ~ 4 hours, preferred 30 minutes ~ 2 hours), obtain a kind of rutile-type nacreous mica pigment.It is do not contain other lead brilliant agent, fully by TiO 2The rutile-type nacreous mica pigment of forming, wherein the clad ratio of rutile titanium dioxide is generally 5 ~ 60% (preferred 6 ~ 50%, more preferably 7 ~ 45%, further preferred 8 ~ 40%).
Al sheet reduction Ti 4+Be reflected in the retort and carry out, the retort vapor pipe inserts liquid seal trough behind a surge tank, when observing the liquid seal trough bubble more after a little while, show that reaction closes to an end, and at this moment, closes vapor pipe, reaction is made solution (lilac) be transferred in the stationary tank subsequent use.Now-making-now-using is wanted in requirement, if keep surpassing 2 hours, and must the inflated with nitrogen seal protection.
Excess coefficient K described here is meant: the actual addition of aluminium flake (by quality or weight) is to make Restore All on the Ti4+ ionic theory of said a part of solubility tetravalent salt of titanium become the K amount doubly of that Theoretical Calculation aluminium flake consumption (by quality or weight) of Ti3+ ionic; For example when K=3 ~ 5, the actual addition of aluminium flake (by quality or weight) should be 3 ~ 5 times of Theoretical Calculation aluminium flake consumption (by quality or weight).
According to the 3rd aspect, the present invention relates to the purposes that above-mentioned rutile-type nacreous mica pigment is applied to makeup, plastics, synthetic leather, printing ink, wallpaper, coating etc.
Can adopt any product that is purchased as the employed synthetic mica powder raw material of base material among the application, to the not special restriction of its granularity.In general, d 50(the cumulative particle sizes percentile reaches 50% o'clock pairing particle diameter, also is meso-position radius or median particle diameter)=5 ~ 600 μ m, preferred 10 ~ 100 μ m, further preferred 15 ~ 40 μ m.This synthetic mica pearly-lustre level preferably as known in the art synthetic mica.
This SnO that do not contain 2The rutile-type nacreous mica pigment have higher whiteness (silvery white series), bright-coloured pigment (iris series and metallic color series) can be widely used in industries such as makeup, plastics, synthetic leather, printing ink, wallpaper, coating.
The present invention has following advantage:
1, under the situation of not introducing other any impurity, obtain a kind of all by TiO 2The synthetic mica pearly pigment of the rutile-type coating of forming;
2, the gloss, the weathering resistance that can be used for pearly pigment of this rutile-type synthetic mica pearly pigment has higher requirements, and can not use and contain the common brilliant agent SnO that leads 2Industry;
3, with the synthetic mica be the pearly pigment of substrate preparation, except that having higher whiteness, also have heatproof, weather resistance preferably, do not contain harmful trace element basically, can be used for high-end fields such as the cosmetics of super quality, car paint.
Embodiment
Embodiment 1
(1) gets the 4mol/L TiCl of 7ml 4Solution, the 5mol/L hydrochloric acid soln of adding 21ml mixes, and is for use;
(2) set Ti 3+The formed TiO of coating 2The per-cent 2% of weight and compound mica weight, promptly P=2% gets the solution that volume is counted V from the solution of step (1), and wherein V (L) confirms according to following calculating:
V=0.0125PW Mica(1+A)/(AC Ti)
=0.0125×2%×100×(1+1/3)/(1/3×4)
=0.025(L);
(3) in V (L) the volume solution that above step (2) is got, add purity greater than 99.5%, thickness is the aluminium flake 1.125g (k=5) of 0.1mm, and reaction obtains the Ti that contains of lilac to there not being bubble 3+Solution;
W Al=9KV?AC Ti/（1+A）
=9×5×0.025×(1/3×4)/(1+1/3)
=1.125(g)
(4) getting 100g (granularity: 10 ~ 60 microns) pearly-lustre level compound mica and electric conductivity is that the 600ml reverse osmosis water stirs and is made into the slurry material less than the reverse osmosis water of 20 μ s/cm by solid-to-liquid ratio 1:6, and is warming up to 85 ℃, and using the Hydrogen chloride adjust pH is 2.2;
(5) in the slurry material of step (4), drip step (3) gained and contain Ti 3+Solution, wherein rate of addition is 0.5L/kg mica h, i.e. 50ml/h keeps pH constant in 2.2 with 20%NaOH solution, up to Ti simultaneously 3+Drips of solution adds;
(6) keep continuing to drip the Ti of 0.5mol/L under uniform temp, the identical pH value condition (85 ℃, pH about 2.2) 4+Solution, wherein rate of addition per hour drips the Ti of 0.25mol by the per kilogram compound mica 4+Meter, promptly feed rate is 50ml/h, is dosed to silvery white standard form and aspect, stops to feed in raw material and (has at this moment added 4mol Ti 4+/ kg compound mica, the clad ratio after the calcining is about 24%), continue constant temperature and stir 10min;
(7) with step (6) gained slurries filtration, with deionized water wash to pH=5 ~ 7,100 ℃ drying 8 hours, 900 ℃ of calcinings 1 hour, obtain a kind of do not contain other lead brilliant agent, fully by TiO 2The synthetic pearly pigment of the rutile-type coating of forming.TiO 2Total clad ratio is about 24%.
With Ai Seli (X-rite) color measurement instrument sensed luminance gloss, form and aspect, fullness of shade, detect the coating substance phase composite with XRD, the result sees table 1.
Embodiment 2
(1) gets the 4mol/LTiCl of 12ml 4Solution, the 5mol/L hydrochloric acid soln of adding 36ml mixes, and is for use;
(2) set Ti 3+The formed TiO of coating 2The per-cent 3.5% of weight and compound mica weight, i.e. P=3.5%,
From the solution of step (1), get the solution of V (L) volume number, wherein V (L) confirms according to following calculating:
V=0.0125PW Mica(1+A)/(AC Ti)
=0.0125×3.5%×100×(1+1/3)/(1/3×4)
=0.04375(L);
(3) in V (L) the volume solution that above step (2) is got, add purity greater than 99.5%, thickness is the aluminium flake 1.575g (k=4) of 0.55mm, and reaction obtains lilac and contains Ti to there not being bubble 3+Solution;
W Al=9KV?AC Ti/（1+A）
=9×4×0.04375×(1/3×4)/(1+1/3)
=1.575(g)
(4) getting 100g (10 ~ 60 microns) pearly-lustre level compound mica and electric conductivity is that the 900ml reverse osmosis water stirs and is made into the slurry material less than the reverse osmosis water of 20 μ s/cm by solid-to-liquid ratio 1:9, and is warming up to 75 ℃, and using the Hydrogen chloride adjust pH is 1.9;
(5) in the slurry material of step (4), drip the Ti that contains of step (3) gained 3+Solution, wherein rate of addition is 0.875L/kg mica h, i.e. 87.5ml/h keeps pH constant about 1.9, up to Ti with 20%NaOH solution simultaneously 3+Drips of solution adds;
(6) keep continuing to drip the Ti of 2.5mol/L under uniform temp, the identical pH value condition (about 75 ℃, pH1.9) 4+Solution, wherein rate of addition per hour drips the Ti of 0.5mol by the per kilogram compound mica 4+Meter, promptly feed rate is 200ml/h, is dosed to silvery white standard form and aspect, stops to feed in raw material and (has at this moment added 4mol Ti 4+/ kg compound mica, the clad ratio after the calcining is about 24%), continue constant temperature and stir 20min;
(7) with step (6) gained slurries filtration, washed to pH=5 ~ 7,100 ℃ drying 10 hours with reverse osmosis water, 900 ℃ of calcinings 1.5 hours, obtain a kind of do not contain other lead brilliant agent, fully by TiO 2The synthetic pearly pigment of the rutile-type coating of forming.TiO 2Total clad ratio is about 24%.
With Ai Seli (X-rite) color measurement instrument sensed luminance gloss, form and aspect, fullness of shade, detect the coating substance phase composite with XRD, the result sees table 1.
Embodiment 3
(1) gets the 4mol/LTiCl of 16ml 4Solution, the 5mol/L hydrochloric acid soln of adding 48ml mixes, and is for use;
(2) set Ti 3+The formed TiO of coating 2The per-cent 5% of weight and compound mica weight, promptly P=5% gets the solution that volume is counted V (L) from the solution of step (1), and wherein V (L) confirms according to following calculating:
V=0.0125PW Mica(1+A)/(AC Ti)
=0.0125×5%×100×(1+1/3)/(1/3×4)
=0.0625(L);
(3) in V (L) the volume solution that above step (2) is got, add purity greater than 99.5%, thickness is the aluminium flake 1.6875g (k=3) of 1mm, and reaction obtains lilac and contains Ti to there not being bubble 3+Solution;
W Al=9KV?AC Ti/（1+A）
=9×3×0.0625×(1/3×4)/(1+1/3)
=1.6875(g)
(4) getting 100g (10 ~ 60 microns) pearly-lustre level compound mica and electric conductivity is that the 1200ml reverse osmosis water stirs and is made into the slurry material less than the reverse osmosis water of 20 μ s/cm by solid-to-liquid ratio 1:12, and is warming up to 65 ℃, and using the Hydrogen chloride adjust pH is 1.6;
(5) in the slurry material of step (4), drip the Ti that contains of step (3) gained 3+Solution, wherein rate of addition is 1.25L/kg mica h, i.e. 125ml/h keeps pH constant with 20%NaOH solution, up to Ti simultaneously 3+Drips of solution adds;
(6) keep continuing to drip the Ti of 4.5mol/L under uniform temp, the identical pH value condition (65 ℃, pH1.6) 4+Solution, wherein rate of addition per hour drips the Ti of 0.75mol by the per kilogram compound mica 4+Meter, promptly feed rate is 166.7ml/h, is dosed to silvery white standard form and aspect, stops to feed in raw material and (has at this moment added 4molTi 4+/ kg compound mica, the clad ratio after the calcining is about 24%), continue constant temperature and stir 30min;
(7) with step (6) gained slurries filtration, washed to pH=5 ~ 7,100 ℃ drying 6 hours with reverse osmosis water, 900 ℃ of calcinings 30 minutes, obtain a kind of do not contain other lead brilliant agent, fully by TiO 2The synthetic pearly pigment of the rutile-type coating of forming.TiO 2Total clad ratio is about 24%.
With Ai Seli (X-rite) color measurement instrument sensed luminance gloss, form and aspect, fullness of shade, detect the coating substance phase composite with XRD, the result sees table 1.
Comparative Examples 3
(1) getting 100g (10 ~ 60 microns) pearly-lustre level compound mica and electric conductivity is that the 1200ml reverse osmosis water stirs and is made into slurry less than the reverse osmosis water of 20 μ s/cm by solid-to-liquid ratio 1:12, and is warming up to 65 ℃, and using the Hydrogen chloride adjust pH is 1.6; Drip the Ti of 4.5mol/L 4+Solution, wherein rate of addition per hour drips the Ti of 0.75mol by the per kilogram compound mica 4+Meter, promptly feed rate is 166.7ml/h, is dosed to silvery white standard form and aspect, stops to feed in raw material and (has at this moment added 4mol Ti 4+/ kg compound mica, the clad ratio after the calcining is about 24%)), continue constant temperature and stir 30min;
(2) with step (5) gained slurries filtration, washed to pH=5 ~ 7,100 ℃ drying 8 hours with reverse osmosis water, 900 ℃ of calcinings 1 hour obtain synthetic pearly pigment.TiO 2Total clad ratio is about 24%.
With Ai Seli (X-rite) color measurement instrument sensed luminance gloss, form and aspect, fullness of shade, detect the coating substance phase composite with XRD, the result sees table 1.
Detected result table 1
Figure BDA00001667469100071
Can find out from above table 1, not use aluminium flake Ti 4+Be reduced to Ti 3+And with Ti 3+On brilliance, form and aspect, fullness of shade, obviously be inferior to the embodiment of the invention 1 ~ 3 as the Comparative Examples of leading brilliant agent 3.

Claims (8)

1. rutile-type synthetic mica pearly pigment, it be through with aluminium flake with a part of solubility titanic (Ti 4+) Ti of salts solution 4+Ion is reduced into Ti 3+Ion and obtain to contain Ti 3+Ion solution is added the above-mentioned Ti of containing then in the slurry material that is formed by synthetic mica and water as base material 3+Ion solution at first is hydrolyzed and realizes preliminary coating, wherein this part solubility titanic (Ti for the weight of synthetic mica 4+) consumption of salts solution should make by Ti 3+The sedimentary TiO of hydrolysis 2Amount for synthetic mica weight 1 ~ 6%, preferred 2 ~ 5%, and then add the solubility titanic (Ti of remainder 4+) salts solution proceeds hydrolysis deposition and further implement coating, wherein the solubility titanic (Ti of this remainder 4+) consumption of salt should make based on total TiO of base material weight 2Clad ratio is 5 ~ 60%, calcines then and finally obtains.
2. rutile-type synthetic mica pearly pigment according to claim 1 is characterized in that the solubility tetravalent salt of titanium is selected from TiCl 4, TiOSO 4In one or both.
3. rutile-type synthetic mica pearly pigment according to claim 1 and 2; It is characterized in that; Said aluminium flake is that purity is greater than 99.5%; The aluminium flake of thickness 0.1 ~ 1mm, its addition are to make Restore All on the Ti4+ ionic theory of said a part of solubility tetravalent salt of titanium become 3 ~ 5 times amount of that Theoretical Calculation aluminium flake consumption of Ti3+ ionic.
4. the preparation method of a rutile-type synthetic mica pearly pigment is characterized in that comprising:
(1) gets the solubility titanic (T of 0.5 ~ 4.5mol/L concentration 4+) hydrochloric acid (v/v) 1:2 ~ 5 by volume of salts solution and 1 ~ 5mol/L concentration, preferred 1:3 mixes and obtains>=obtain solution of V (L) volume;
(2) get the above-mentioned obtain solution of V (L) volume in the middle of the obtain solution that obtains from step (1), wherein volume V confirms according to following formula:
V=0.0125PW Mica(1+A)/(AC Ti)
P: in following steps (5) by containing Ti 3+Solution water separate the formed TiO of coating 2The per-cent of weight and compound mica weight; General P=1 ~ 6%, preferred P=2 ~ 5%;
W Mica: the consumption of compound mica, g;
A: solubility titanic (Ti 4+) volume ratio of salts solution and hydrochloric acid soln, be generally 1:2 ~ 5, preferred 1:3;
C Ti: solubility titanic (Ti 4+) volumetric molar concentration of salts solution, be generally 0.5 ~ 4.5mol/L;
(3) calculate according to following formula, add W in the solution of in step (2), being got AlAluminium flake, the reaction to there not being bubble, promptly obtain the Ti that contains of lilac 3+Solution;
W Al=9KVAC Ti/（1+A）
W Al: need be with the amount of aluminium flake, g;
V: need reductive Ti 4+The volume number of salts solution, L;
K: excess coefficient, K=3 ~ 5;
A:Ti 4+The volume ratio of salts solution and hydrochloric acid soln is generally 1:2 ~ 5, preferred 1:3;
C Ti: Ti 4+The volumetric molar concentration of salts solution is generally 0.5 ~ 4.5mol/L;
(4) get some amount (W MicaGram) pearly-lustre level compound mica and water (preferably specific conductivity is less than the reverse osmosis water of 20 μ s/cm or the specific conductivity deionized water less than 50 μ s/cm); Be made into the slurry material by solid-to-liquid ratio 1:6 ~ 12 stirrings; Under whipped state, the slurry material is warming up to 65 ~ 85 ℃, using Hydrogen chloride to regulate the pH value is 1.6 ~ 2.2;
(5) in the slurry material that above step (4) is obtained, drip the Ti that contains of step (3) gained 3+Solution, wherein rate of addition be the per kilogram compound mica per hour 0.5 ~ 1.25L contain Ti 3+Solution, the pH value stabilization that keeps system with alkali simultaneously is 1.6 ~ 2.2, up to containing Ti 3+Solution addition till;
(6) keep continuing to drip the Ti of 0.5 ~ 4.5mol/L concentration under uniform temp, the identical pH condition 4+Salts solution, wherein rate of addition per hour drips the Ti of 0.25 ~ 0.75mol by the per kilogram compound mica 4+Come to confirm, be dosed to required form and aspect always after, stop to feed in raw material, continue constant temperature then and stir 10 ~ 30min;
(7) with step (6) gained slurries filtration, washing to pH=5 ~ 7 with reverse osmosis water, is dry under 100 ~ 150 ℃ of conditions in temperature, and 500 ~ 900 ℃ of calcinings obtain the rutile-type nacreous mica pigment.
5. the preparation method of rutile-type synthetic mica pearly pigment according to claim 4 is characterized in that, the clad ratio of rutile titanium dioxide is 5 ~ 60%.
6. the preparation method of rutile-type synthetic mica pearly pigment according to claim 4 is characterized in that the solubility tetravalent salt of titanium is selected from TiCl 4, TiOSO 4In one or both.
7. the preparation method of rutile-type synthetic mica pearly pigment according to claim 4 is characterized in that, said aluminium flake is a purity greater than 99.5%, the aluminium flake of thickness 0.1 ~ 1mm.
8. each rutile-type nacreous mica pigment of claim 1 ~ 3 is applied to the purposes of makeup, plastics, synthetic leather, printing ink, wallpaper or coating.
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Citations (10)

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CN101279764A (en) * 2008-04-25 2008-10-08 陕西科技大学 Preparation of red schorl type nano-titanic oxide
CN101343424A (en) * 2008-08-26 2009-01-14 攀钢集团研究院有限公司 Pearlescent pigment and preparation thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341291A (en) * 1963-10-04 1967-09-12 British Titan Products Production of titanium dioxide
CN1216997A (en) * 1996-03-29 1999-05-19 博里利斯股份公司 Composition contg. magnesium, titanium, halogen and inner electron donor, its prepn. and use for polymerization of alpha-olefins
CN1352669A (en) * 1999-03-08 2002-06-05 默克专利股份有限公司 Methods and compositions related to pearlescent pigments
CN1336327A (en) * 2000-08-02 2002-02-20 湖南株洲化工集团有限责任公司 Process of producing high-purity magnetic iron oxide with ferous sulfate as by-product of titanium white production
CN1364833A (en) * 2002-02-09 2002-08-21 中国科学院上海硅酸盐研究所 Process for preparing rutile phase nano titanium dioxide
CN101085882A (en) * 2006-06-08 2007-12-12 默克专利股份有限公司 Effect pigments
CN101235227A (en) * 2008-03-13 2008-08-06 北京首创纳米科技有限公司 Method for preparing mica titanium nacreous material
CN101279764A (en) * 2008-04-25 2008-10-08 陕西科技大学 Preparation of red schorl type nano-titanic oxide
CN101343424A (en) * 2008-08-26 2009-01-14 攀钢集团研究院有限公司 Pearlescent pigment and preparation thereof
CN101768379A (en) * 2009-12-29 2010-07-07 福州坤彩精化有限公司 Method for preparing glass-based pearlescent pigment with high luster and high weatherability

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