CN102660157A - Large-sized synthesized mica pearlescent pigment and preparation method thereof - Google Patents
Large-sized synthesized mica pearlescent pigment and preparation method thereof Download PDFInfo
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- CN102660157A CN102660157A CN2012101606024A CN201210160602A CN102660157A CN 102660157 A CN102660157 A CN 102660157A CN 2012101606024 A CN2012101606024 A CN 2012101606024A CN 201210160602 A CN201210160602 A CN 201210160602A CN 102660157 A CN102660157 A CN 102660157A
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Abstract
The invention relates to a large-sized synthesized mica pearlescent pigment, which is characterized in that large-sized synthesized mica powder with d50 being equal to 50 to 600 micrometers is adopted as a substrate, wherein a high-refraction oxide membrane is arranged on the surface of the substrate, the high-refraction oxide membrane is formed by implementing the hydrolysis enveloping adopting soluble salt which can be hydrolyzed into high-refraction oxide as a hydrolysis precursor under the existence of soluble trivalent aluminum salt which is used as a depositing agent. The invention also relates to a preparation method of the large-sized synthesized mica pearlescent pigment. The large-sized synthesized mica pearlescent pigment has strong star-like twinkling property and good decoration effect and can be widely applied to the industries such as cosmetics, synthesized leather, plastics, texture costumes, paint and the like.
Description
Technical field
The present invention relates to a kind of big particle diameter synthetic mica pearly pigment and preparation method thereof, belong to inorganic non-metallic effect pigment field.
Background technology
In recent years, be the pearly pigment of base material with the synthetic mica, progressively be widely used with its high whiteness (silvery white series), (iris and metallic color series) bright in luster, no hazardous trace elements, premium properties such as high temperature resistant, "dead".Especially particle diameter is the big particle diameter synthetic mica pearly pigment of 50 ~ 1000 μ m, has superpower flickering, has more special decorative effect.In this big particle size range, natural mica is variegated quality that badly influences the mica-based pearly pigment inevitably; With the glass flakes is the pearly pigment of base material, frangible and the stimulation of skin limited its use range because of its base material.The big particle diameter pearly pigment of synthetic mica overcomes the shortcoming of above-mentioned two kinds of base materials, has good toughness, and fabulous whiteness, superpower flickering are arranged again simultaneously.But in the preparation of big particle diameter synthetic mica pearly pigment, a big technical barrier being arranged, promptly is that big particle diameter compound mica is bigger because of its particle diameter, and specific surface area is little; Grinding time is short, and surfactivity is poor, makes that the hydrolysis coating is difficult to carry out; When causing coating, produce a large amount of episome TiO
2, have a strong impact on the quality of pearly pigment, even do not produce pearl effect.Chinese patent CN200410065315.0 is a base material with the natural mica, adopt to add zinc salt hydrolysis coating and prepares big particle diameter natural mica pearly pigment, and identical method also is not suitable for the preparation of big particle diameter synthetic mica pearly pigment; Chinese patent CN200510020568.0 and Chinese patent CN00820062.9 disclose the preparation method of synthetic mica pearly pigment; The technology of preparing that does not relate to big particle diameter synthetic mica pearly pigment can not solve the technology of preparing difficult problem of big particle diameter synthetic mica pearly pigment equally.
JP7157687A (06 month 20 days nineteen ninety-five) discloses the working method of flaring pearlescent pigment, and it comprises at first cladding titanium dioxide on the mica substrate, in the presence of the urea as the precipitation agent of cobalt salt and aluminium salt, forms cobalt-al oxide layer from the teeth outwards then.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of big particle diameter synthetic mica pearly pigment and preparation method thereof is provided.
According to the present invention, following technical scheme is provided:
1. one kind big particle diameter synthetic mica pearly pigment is characterized in that it is with d
50(the cumulative particle sizes percentile reaches 50% o'clock pairing particle diameter; Also be meso-position radius or median particle diameter)=50 ~ 600 μ m (preferred 100 ~ 500 μ m; Further preferred 200 ~ 400 μ m) big particle diameter compound mica is a base material; The oxide film that on the surface of this base material, has high refractive index, this film are that the soluble salt that generates high refractive index oxide with hydrolyzable at base material and in the presence of as the solubility trivalent aluminium salt of deposition agent is that the hydrolysis presoma is hydrolyzed coating and on base material, forms.
2. according to above the 1st described big particle diameter synthetic mica pearly pigment, it is characterized in that in the hydrolysis coating, (preferred 3 ~ 5g further preferred 3.5 ~ 4.5g) presses Al to the add-on of trivalent aluminium salt for the per kilogram compound mica adds 2 ~ 6g
3+The solubility trivalent aluminium salt of meter.
3. according to above the 2nd described big particle diameter synthetic mica pearly pigment, it is characterized in that the clad ratio of hydrolysis coating is 5 ~ 45%, preferred 6.5 ~ 30%, further preferred 10 ~ 25%.Clad ratio described here is a term commonly used in the prior art, generally is meant the weight percent of coating layer for the weight of the base material that is coated.
4. according to above the 1st described big particle diameter synthetic mica pearly pigment, it is characterized in that above-mentioned aluminum soluble salt is selected from one or more in crystallization aluminum chloride, aluminum nitrate, the Tai-Ace S 150 etc.
5. according to each above the 1st ~ 4 described big particle diameter synthetic mica pearly pigment, it is characterized in that above-mentioned high refractive index oxide (n>1.8) be selected from TiO
2, SnO
2, Fe
2O
3, ZnO, ZrO
2In one or more.
6. according to each above the 1st ~ 4 described big particle diameter synthetic mica pearly pigment, it is characterized in that above-mentioned hydrolyzable generates high refractive index oxide (RI n>1.8) soluble salt be selected from: TiCl
4, TiOSO
4, SnCl
4, FeCl
3, FeSO
4, Zn (NO
3)
2, ZnCl
2, ZnSO
4, ZrOCl
2In one or more.
7. according to the preparation method of above the 1st described big particle diameter synthetic mica pearly pigment, it is characterized in that may further comprise the steps:
(1), be d with particle diameter
50=50 ~ 600 μ m (preferred 100 ~ 500 μ m; Further preferred 200 ~ 400 μ m) the big particle diameter compound mica and the water of (detection of Ma Erwen laser particle analyzer); 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 slurry, under whipped state, slurry be warming up to 70 ~ 90 ℃ by solid-to-liquid ratio 1:5 ~ 11.5 stirrings;
(2), press per kilogram compound mica adding (for example disposable adding) and press Al
3+(concentration of aluminum salt solution is 10 ~ 30wt% to meter 2 ~ 6g for preferred 3 ~ 5g, further preferred 3.5 ~ 4.5g) solubility trivalent aluminium salt, continues constant temperature and stirs 10 ~ 30min;
(3), with Hydrogen chloride the pH value is transferred to 1.6 ~ 3.5; By the per hour reinforced 0.1 ~ 0.8mol of per kilogram compound mica, be that the soluble salt solution that 0.5 ~ 4.0mol/L hydrolyzable generates high refractive index oxide (n>1.8) slowly adds in the slurry with concentration, constant with 2mol/L sodium hydroxide or ammoniacal liquor maintenance pH simultaneously; Under constant temperature, constant pH (i.e. 70 ~ 90 ℃ and pH 1.6 ~ 3.5); Be dosed to required form and aspect, stop to feed in raw material, continue constant temperature and stir 10 ~ 30min;
(4), with step (3) gained slurries filtration, wash to pH=5 ~ 7 with reverse osmosis water, be 100 ~ 150 ℃ of dryings in temperature, 500 ~ 900 ℃ (preferred 600 ~ 860 ℃, further preferred 700 ~ 800 ℃) calcining obtains big particle diameter (d
50=50 ~ 600 μ m) synthetic mica pearly pigment.
8. according to the preparation method of above the 7th described big particle diameter synthetic mica pearly pigment, it is characterized in that above-mentioned aluminum soluble salt is selected from one or more in crystallization aluminum chloride, aluminum nitrate, the Tai-Ace S 150 etc.; Above-mentioned high refractive index oxide (n>1.8) be selected from TiO
2, SnO
2, Fe
2O
3, ZnO, ZrO
2In one or more; Above-mentioned hydrolyzable generates high refractive index oxide (RI n>1.8) soluble salt be selected from: TiCl
4, TiOSO
4, SnCl
4, FeCl
3, FeSO
4, Zn (NO
3)
2, ZnCl
2, ZnSO
4, ZrOCl
2In one or more.
9. according to the preparation method of above the 7th described big particle diameter synthetic mica pearly pigment; It is characterized in that; The feeding quantity of soluble salt generally is 0.625mol ~ 5.625mol/ per kilogram mica powder, and the coating clad ratio that the calcining back forms is about 5 ~ 45%, preferred 6.5 ~ 30%, further preferred 10 ~ 25%.
10. the purposes that is used for makeup, synthetic leather, plastics, textile garment or paint according to any one described big particle diameter synthetic mica pearly pigment in above the 1st ~ 6 or by the big particle diameter synthetic mica pearly pigment that method obtained of any one in above 7 ~ 9.
Can adopt any product that is purchased as the employed big particle diameter synthetic mica powder raw material of base material among the application.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)=50 ~ 600 μ m, preferred 100 ~ 500 μ m, further preferred 200 ~ 400 μ m.
Behind the big particle diameter synthetic mica of the gained pearly pigment card-coating, adopt the CIE LCH color model of Ai Seli x-rite to detect form and aspect colourity.
That this big particle diameter synthetic mica pearly pigment has is superpower, the flickering as the star, has fabulous decorative effect, can be widely used in industries such as makeup, synthetic leather, plastics, textile garment, paint.
The present invention has the following advantages:
1, utilizes " the multivalent metal cation effect " of aluminium salt; Changed the electronegativity on big particle diameter compound mica surface; Quickened the sedimentation of hydrolysis presoma material, solved because big particle diameter compound mica specific surface area is little, surfactivity difference and can not prepare the technical barrier of the synthetic pearly pigment of the big particle diameter of high-quality;
2, the Al of aluminium salt
3+Have and make titanium dioxide crystal form convert the brilliant effect of leading of rutile-type into by anatase titanium dioxide; In the pearly pigment preparation of using titanium salt as hydrolysis coating presoma; Rutile titanium dioxide has higher specific refractory power, and better weather resistance is corrosion-resistant; Make that its pearly pigment brightness is better, have more and have been widely used.
3, through the check of Ai Seli (x-rite) color measurement instrument, adopt CIE LCH color model to estimate, the big particle diameter pearly pigment of gained of the present invention has higher whiteness, fullness of shade and purer tone.
Embodiment
Below further specify the present invention through embodiment, wherein said raw material umber is parts by weight or weight percent except that specified otherwise.
Embodiment 1
(1) takes by weighing d
50The compound mica 100g of=50 μ m, adding specific conductivity by solid-liquid 1:11.5 is the reverse osmosis water 1150ml of 20 μ s/cm, it is 70 ℃ that intensification limit, limit is stirred to temperature;
(2) in step (1) gained suspension-s, press the per kilogram compound mica and add 2 gram Al
3+Count, promptly add the crystal aluminum chloride (AlCl of concentration 20wt%
3H
2O) solution 9 grams, 70 ℃ of constant temperature stir 10min;
(3) under 70 ℃ of temperature; Using Hydrogen chloride to regulate the pH value is 1.6; The titanium tetrachloride that with concentration is 4mol/L evenly adds in step (2) suspension-s with the feed rate of 0.8mol/kg synthetic mica h (being 20ml/h) lentamente; Drip the sodium hydroxide solution that concentration is 20wt% simultaneously, to keep the constant about 1.6 of pH value.When being dosed to silvery white pearly pigment standard specimen form and aspect, stop to feed in raw material (for the 100g compound mica, at this moment having added the 0.225mol soluble salt), continue constant temperature and stir 10min;
(4) with step (3) gained slurries filtration, washing to pH=5 ~ 7 with reverse osmosis water, is dry under 100 ± 5 ℃ of conditions in temperature, and 900 ℃ of calcinings obtain a kind of big particle diameter (d
50=50 μ m) silvery white synthetic mica pearly pigment, the TiO of formation
2Coating is about 15% with respect to the clad ratio of compound mica.
Behind the big particle diameter synthetic mica of the gained pearly pigment card-coating, adopt the CIE LCH color model of Ai Seli x-rite to detect form and aspect colourity.Detected result is seen table 1.
Embodiment 2
(1) takes by weighing d
50The compound mica 100g of=325 μ m presses solid-liquid 1:8.25 and adds the deionized water 825ml of specific conductivity less than 50 μ s/cm, and it is 80 ℃ that intensification limit, limit is stirred to temperature;
(2) in step (1) gained suspension-s, press the per kilogram compound mica and add 4 gram Al
3+Count, promptly add the crystal aluminum chloride (AlCl of concentration 10wt%
3H
2O) solution 36 grams, 80 ℃ of constant temperature stir 20min;
(3) under 80 ℃ of temperature; Using Hydrogen chloride to regulate the pH value is 1.9; The titanium tetrachloride that with concentration is 2.25mol/L evenly adds in step (2) suspension-s with the feed rate of 0.45mol/kg synthetic mica h (being 20ml/h) lentamente; Drip concentration simultaneously and be 20% sodium hydroxide solution, to keep the constant about 1.9 of pH value.When being dosed to silvery white pearly pigment standard specimen form and aspect (for the 100g compound mica, at this moment having added the 0.1mol soluble salt), stop to feed in raw material, continue constant temperature and stir 20min;
(4) with step (3) gained slurries filtration, washing to pH=5 ~ 7 with reverse osmosis water, is dry under 125 ± 5 ℃ of conditions in temperature, and 700 ℃ of calcinings obtain a kind of big particle diameter (d
50=325 μ m) silvery white synthetic mica pearly pigment, the TiO of formation
2Coating is about 7% with respect to the clad ratio of compound mica.
Behind the big particle diameter synthetic mica of the gained pearly pigment card-coating, adopt the CIE LCH color model of Ai Seli x-rite to detect form and aspect colourity.Detected result is seen table 1.
Embodiment 3
(1) takes by weighing d
50The compound mica 100g of=600 μ m, adding specific conductivity by solid-liquid 1:5 is the reverse osmosis water 500ml of 20 μ s/cm, it is 90 ℃ that intensification limit, limit is stirred to temperature;
(2) in step (1) gained suspension-s, press the per kilogram compound mica and add 6 gram Al
3+Meter promptly adds concentration 30wt% crystal aluminum chloride (AlCl
3H
2O) solution 18 grams, 90 ℃ of constant temperature stir 30min;
(3) under 90 ℃ of temperature; Using Hydrogen chloride to regulate the pH value is 2.2; The titanium tetrachloride that with concentration is 0.5mol/L evenly adds in step (2) suspension-s with the feed rate of 0.1mol/kg synthetic mica h (being 20ml/h) lentamente; Drip concentration simultaneously and be 20% sodium hydroxide solution, to keep the constant about 2.2 of pH value.When being dosed to silvery white pearly pigment standard specimen form and aspect (for the 100g compound mica, at this moment having added the 0.0625mol soluble salt), stop to feed in raw material, continue constant temperature and stir 30min;
(4) with step (3) gained slurries filtration, washing to pH=5 ~ 7 with reverse osmosis water, is dry under 150 ℃ of conditions in temperature, and 500 ℃ of calcinings obtain a kind of big particle diameter (d
50=600 μ m) silvery white synthetic mica pearly pigment, the TiO of formation
2Coating is about 4.55% with respect to the clad ratio of compound mica.
Behind the big particle diameter synthetic mica of the gained pearly pigment card-coating, adopt the CIE LCH color model of Ai Seli x-rite to detect form and aspect colourity.Detected result is seen table 1.
Embodiment 4
(1) takes by weighing d
50The compound mica 100g of=50 μ m presses solid-liquid 1:11.5 and adds the deionized water 1150ml of specific conductivity less than 50 μ s/cm, and it is 70 ℃ that intensification limit, limit is stirred to temperature;
(2) in step (1) gained suspension-s, press the per kilogram compound mica and add 2 gram Al
3+Count, promptly add the crystal aluminum chloride (AlCl of concentration 20wt%
3H
2O) solution 9 grams, 70 ℃ of constant temperature stir 10min;
(3) under 70 ℃ of temperature; Using Hydrogen chloride to regulate the pH value is 3.5; The iron trichloride that with concentration is 1mol/L evenly adds in step (2) suspension-s with the feed rate of 0.8mol/kg synthetic mica h (being 20ml/h) lentamente; Drip concentration simultaneously and be 20% sodium hydroxide solution, to keep the constant about 3.5 of pH value.When being dosed to bronze-colored pearly pigment standard specimen form and aspect, stop to feed in raw material (for the 100g compound mica, at this moment having added the 0.3mol soluble salt), continue constant temperature and stir 10min;
(4) with step (3) gained slurries filtration, washing to pH=5 ~ 7 with reverse osmosis water, is dry under 100 ± 5 ℃ of conditions in temperature, and 550 ℃ of calcinings obtain a kind of big particle diameter (d
50=50 μ m) bronze-colored synthetic mica pearly pigment, the Fe of formation
2O
3Coating is 18% with respect to the clad ratio of compound mica.
Behind the big particle diameter synthetic mica of the gained pearly pigment card-coating, adopt the CIE LCH color model of Ai Seli x-rite to detect form and aspect colourity.Detected result is seen table 1.
Comparative Examples 1: do not add aluminium salt, other is identical with embodiment 3.
(1) takes by weighing d
50The compound mica 100g of=600 μ m, adding specific conductivity by solid-liquid 1:5 is the reverse osmosis water 500ml of 20 μ s/cm, it is 90 ℃ that intensification limit, limit is stirred to temperature;
(2) under 90 ℃ of temperature; Using Hydrogen chloride to regulate the pH value is 2.2; The titanium tetrachloride that with concentration is 0.5mol/L evenly adds in step (2) suspension-s with the feed rate of 0.1mol/kg synthetic mica h (being 20ml/h) lentamente; Drip concentration simultaneously and be 20% sodium hydroxide solution, to keep the constant about 2.2 of pH value.When being dosed to silvery white pearly pigment standard specimen form and aspect, stop to feed in raw material (for the 100g compound mica, at this moment having added the 0.0625mol soluble salt), continue constant temperature and stir 30min;
(3) with step (2) gained slurries filtration, washing to pH=5 ~ 7 with reverse osmosis water, is dry under 150 ℃ of conditions in temperature, and 500 ℃ of calcinings obtain a kind of big particle diameter (d
50=600 μ m) silvery white synthetic mica pearly pigment, the TiO of formation
2Coating is 4.5% with respect to the clad ratio of compound mica.
Behind the big particle diameter synthetic mica of the gained pearly pigment card-coating, adopt the CIE LCH color model of Ai Seli x-rite to detect form and aspect colourity.Detected result is seen table 1.
CIE LCH color model detected result (x-rite) table 1
Can find out to have at embodiment 3 and on colourimetric number, obviously be superior to not using the Comparative Examples 1 of solubility trivalent aluminium salt as deposition agent as the high refractive index oxide of the formation down film of the solubility trivalent aluminium salt of deposition agent from the comparison of last table 1 embodiment 3 and Comparative Examples 1.
Claims (10)
1. one kind big particle diameter synthetic mica pearly pigment is characterized in that it is with d
50The big particle diameter compound mica of=50 ~ 600 μ m is a base material; The oxide film that on the surface of this base material, has high refractive index, this film are that the soluble salt that generates high refractive index oxide with hydrolyzable at base material and in the presence of as the solubility trivalent aluminium salt of deposition agent is that the hydrolysis presoma is hydrolyzed coating and on base material, forms.
2. big particle diameter synthetic mica pearly pigment according to claim 1 is characterized in that, in the hydrolysis coating, the add-on of trivalent aluminium salt is that Al is pressed in the adding of per kilogram (kg) compound mica
3+The solubility trivalent aluminium salt of meter 2 ~ 6g.
3. big particle diameter synthetic mica pearly pigment according to claim 2 is characterized in that the clad ratio of hydrolysis coating is 5 ~ 45%, preferred 6.5 ~ 30%.
4. big particle diameter synthetic mica pearly pigment according to claim 1 is characterized in that said aluminum soluble salt is selected from one or more in crystallization aluminum chloride, aluminum nitrate, the Tai-Ace S 150 etc.
5. according to each described big particle diameter synthetic mica pearly pigment of claim 1 ~ 4, it is characterized in that the oxide compound of said high refractive index is selected from TiO
2, SnO
2, Fe
2O
3, ZnO, ZrO
2In one or more.
6. according to each described big particle diameter synthetic mica pearly pigment of claim 1 ~ 4, it is characterized in that the soluble salt that said hydrolyzable generates high refractive index oxide is selected from: TiCl
4, TiOSO
4, SnCl
4, FeCl
3, FeSO
4, Zn (No
3)
2, ZnCl
2, ZnSO
4, ZrOCl
2In one or more.
7. the preparation method of the big particle diameter synthetic mica pearly pigment of claim 1 is characterized in that may further comprise the steps:
(1), be d with particle diameter
50Big particle diameter compound mica and the water of=50 ~ 600 μ m, preferred specific conductivity, is made into slurry, under whipped state, slurry is warming up to 70 ~ 90 ℃ by solid-to-liquid ratio 1:5 ~ 11.5 stirrings less than the deionized water of 50 μ s/cm less than the reverse osmosis water of 20 μ s/cm or specific conductivity;
(2), press the adding of per kilogram compound mica and press Al
3+The solubility trivalent aluminium salt of meter 2 ~ 6g, wherein the concentration of aluminum salt solution is 10 ~ 30wt%, continues constant temperature and stirs 10 ~ 30min;
(3), with Hydrogen chloride the pH value is transferred to 1.6 ~ 3.5; By the per hour reinforced 0.1 ~ 0.8mol of per kilogram compound mica, be that the soluble salt solution that 0.5 ~ 4.0mol/L hydrolyzable generates high refractive index oxide slowly adds in the slurry with concentration, constant with 2mol/L sodium hydroxide or ammoniacal liquor maintenance pH simultaneously; Under constant temperature, constant pH; Be dosed to required form and aspect, stop to feed in raw material, continue constant temperature and stir 10 ~ 30min;
(4), with step (3) gained slurries filtration, wash to pH=5 ~ 7 with reverse osmosis water, be 100 ~ 150 ℃ of dryings in temperature, 500 ~ 900 ℃ of calcinings obtain big particle diameter synthetic mica pearly pigment.
8. the preparation method of big particle diameter synthetic mica pearly pigment according to claim 7 is characterized in that said aluminum soluble salt is selected from one or more in crystallization aluminum chloride, aluminum nitrate, the Tai-Ace S 150 etc.; Said high refractive index oxide is selected from TiO
2, SnO
2, Fe
2O
3, ZnO, ZrO
2In one or more; The soluble salt that said hydrolyzable generates high refractive index oxide is selected from: TiCl
4, TiOSO
4, SnCl
4, FeCl
3, FeSO
4, Zn (NO
3)
2, ZnCl
2, ZnSO
4, ZrOCl
2In one or more.
9. the preparation method of big particle diameter synthetic mica pearly pigment according to claim 7 is characterized in that, in step (3), is dosed to the clad ratio that behind calcining step, obtains 5 ~ 45%, preferred 6.5 ~ 30% high refractive index oxide.
10. the purposes that is used for makeup, synthetic leather, plastics, textile garment or paint according to the big particle diameter synthetic mica pearly pigment of claim 1 ~ 6 or by the big particle diameter synthetic mica pearly pigment that any one described method obtained in the claim 7 ~ 9.
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| CN103540171A (en) * | 2013-10-11 | 2014-01-29 | 南京理工大学 | Preparation method of single-coating cobalt titanate green/mica pearlescent composite pigment |
| CN104263017A (en) * | 2014-09-24 | 2015-01-07 | 南阳市凌宝珠光颜料有限公司 | Method for preparing iron-series pigment with crystal effect |
| CN104870571A (en) * | 2012-12-20 | 2015-08-26 | 默克专利股份有限公司 | Pigments |
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| CN105504889A (en) * | 2016-01-14 | 2016-04-20 | 广西七色珠光材料股份有限公司 | Gold-series low-glossiness laminated pigment and preparation method thereof |
| CN107325589A (en) * | 2017-07-05 | 2017-11-07 | 江苏贝丽得新材料有限公司 | A kind of glittering Gold production effect pearlescent pigment of high-purity titanium ferroalloy and preparation method thereof |
| CN107641339A (en) * | 2017-10-27 | 2018-01-30 | 河北欧克精细化工股份有限公司 | Changeable colors along with angle stereoscopic series feature pearlescent pigment and its preparation technology and purposes |
| CN109394556A (en) * | 2018-12-27 | 2019-03-01 | 林中 | A kind of sun-proof powder and preparation method thereof |
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