CN104893366B - A kind of magnetic pearlescent pigment with 3D effect and preparation method thereof - Google Patents
A kind of magnetic pearlescent pigment with 3D effect and preparation method thereof Download PDFInfo
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- CN104893366B CN104893366B CN201510340610.0A CN201510340610A CN104893366B CN 104893366 B CN104893366 B CN 104893366B CN 201510340610 A CN201510340610 A CN 201510340610A CN 104893366 B CN104893366 B CN 104893366B
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- 239000000049 pigment Substances 0.000 title claims abstract description 89
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 62
- 230000000694 effects Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 90
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 23
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000011241 protective layer Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- 239000002585 base Substances 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 229910052681 coesite Inorganic materials 0.000 claims description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims description 23
- 229910052682 stishovite Inorganic materials 0.000 claims description 23
- 229910052905 tridymite Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000001105 regulatory effect Effects 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000005022 packaging material Substances 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000004753 textile Substances 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 7
- 229940056319 ferrosoferric oxide Drugs 0.000 abstract description 7
- 231100000749 chronicity Toxicity 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910020489 SiO3 Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 241000122205 Chamaeleonidae Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen sodium oxide Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C09C1/40—Compounds of aluminium
-
- 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
- C09C1/28—Compounds of silicon
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
Abstract
A kind of magnetic pearlescent pigment with 3D effect and preparation method thereof; described magnetic pearlescent pigment includes pearlescent pigment, the magnetic clad being made up of cobalt oxide, ferrum oxide and ferrous oxide on pearlescent pigment layer, the protective layer on magnetic clad, and wherein pearlescent pigment includes base material and one or more layers pearlescent pigment layer.3D magnetic series pearlescent pigment prepared by the present invention utilize surface magnetism material walk magnetic phenomenon can produce solid, illusion 3D effect.The preparation method of the 3D magnetic series pearlescent pigment of the present invention, the difficult problem that the ferrous iron existed in prior art is easily oxidized can be overcome, reduce ferroso-ferric oxide loss, reduce magnetic losses, and the part cobalt acid ferrum of generation is stably not easily oxidized so that the preservation of pigment has chronicity.
Description
Technical field
The present invention relates to a kind of magnetic pearlescent pigment, particularly a kind of magnetic series pearlescent pigment with 3D visual effect and preparation method thereof, belong to ornamental effect pigment field.
Background technology
3D magnetic series pearlescent pigment refers to that being coated with one layer outside base material has magnetic material, utilize magnetic material to arrange under Action of Static Magnetic Field, coupling, the behavior such as migration walk magnetic feature, in the ornamental pearlescent pigment application such as printing or spraying, it is positioned in magnetostatic field when coating not surface drying completely, the very witty dreamlike 3D effect with glittering gloss can be produced.This product is widely used in the 3D effect of cosmetics, synthetic leather, glass technology, printing-ink, printing in textiles, packaging material, artware etc. and builds.
Existing technology is mainly by Fe3O4Pigment is made to produce three-dimensional 3-D effect as magnetic material.It is with the slide of low-refraction for base material, is coated with the metal-oxide (or being alternately coated with high index of refraction and low-refraction oxide) of one or more layers high index of refraction and obtains the pearlescent pigment that different colours is serial, is coated with Fe on this basis again3O4As magnetic material, thus obtaining bright and colourful 3D magnetic pearlescent pigment.As Chinese patent CN102766357A describes with ferrous chloride for raw material, potassium chlorate is oxidant, selects the method that oxidation-precipitation method prepares ferroso-ferric oxide.Utilize this characteristic of ferroso-ferric oxide, with pearlescent pigment for base material at one layer of nanoscale ferroso-ferric oxide of its coated with uniform, so that pigment has magnetic characteristic.And for example Chinese patent CN101445674A discloses a kind of magnetic pearlescent pigment and preparation method thereof.This preparation method is by configuring the Fe of certain mol proportion3+And Fe2+Solution, pours in this mixed liquor by substrate, makes Fe by regulating pH value3O4It is coated on substrate surface.
In above two invention, no matter utilize potassium chlorate to generate ferroso-ferric oxide as oxidant or Direct precipitation reaction generates ferroso-ferric oxide, all exist and be difficult to accurately control Fe3+And Fe2+The problem of ratio, potassium chlorate oxidation can not generate Fe accurately3+(by dioxygen oxidation in air), and adopt Fe3+And Fe2+Mixing cladding, reaction and last handling process in, part Fe2+Fe can be oxidized to3+, thus result in that surface of pigments magnetic is weak does not even produce magnetic, affect pigment complexion effect simultaneously.
Summary of the invention
For above-mentioned problem of the prior art; inventors performed further investigation; found that; having magnetic clad by being coated with one layer on finished product pearlescent pigment, this magnetic clad is the permanent magnet material of Conjugate ferrite, and its component can accurately control; can't be oxidized when washing, drying; the thin layer being then coated with one layer of low-refraction again is used as protective layer, obtains a kind of magnetic series pearlescent pigment with stable 3D effect, this completes the present invention.
The magnetic series pearlescent pigment with 3D effect of the present invention; it includes pearlescent pigment, the magnetic clad being made up of cobalt oxide, ferrum oxide and ferrous oxide on pearlescent pigment layer, the protective layer on magnetic clad, and wherein pearlescent pigment includes base material and one or more layers pearlescent pigment layer.
Wherein, cobalt oxide, ferrous oxide, ferrum oxide the ratio of clad ratio be (1～5): (1～5): (0.1～10), preferably (1～3): (1～5): (0.5～8), more preferably 1:(1～5): (0.5～2.5).
Preferably, the weight of the described 3D stereoeffect each component of series of magnetic pearlescent pigment is:
Wherein, pearlescent pigment can be commercially available pearlescent pigment, or use the base materials such as natural mica, synthetic mica, tabular alumina, lamellar silicon oxide, glass flake to be coated with one or more layers pearlescent pigment layer to obtain, it is possible to be the substrate material cladding SnO such as natural mica, synthetic mica, tabular alumina, lamellar silicon oxide, glass flake2、TiO2、SiO2And Fe2O3Deng the pearlescent pigment that the combination in any rete of four kinds of materials is obtained, such as (but not limited to):
Base material+TiO2Layer, base material+SnO2Layer+TiO2Layer, base material+SnO2Layer+TiO2Layer+SiO2Layer+TiO2Layer, base material+SnO2Layer+TiO2Layer+SiO2Layer+SnO2Layer+TiO2Layer, base material+TiO2Layer+Fe2O3Layer, base material+TiO2Layer+SiO2Layer+Fe2O3Layer, base material+TiO2Layer/Fe2O3Layer, base material+TiO2Layer/Fe2O3Layer+SiO2Layer+TiO2Layer/Fe2O3Layer, base material+Fe2O3Layer, base material+Fe2O3Layer+TiO2Layer, base material+Fe2O3Layer+SiO2Layer+Fe2O3Layer, base material+TiO2Layer+SiO2Layer+TiO2Layer etc..Preferred silvery white is serial, iris is serial, gold is serial, color system, ferrum series, diamond are serial, chameleon series pearlescent pigment, it is preferred that silvery white serial, iris is serial, golden serial, ferrum series pearlescent pigment.
Described protective layer can be SiO2、MgO、Al2O3、MgF2、AlF3And their combination in any, it is preferable that SiO2、Al2O3.Protective layer is preferably included in the alumina layer on magnetic clad and the silicon dioxide layer on alumina layer.
The above-mentioned magnetic series pearlescent pigment with 3D effect, wherein, if with pearlescent pigment for 100 parts by weight, Conjugate ferrite can be 0.21-20 part, preferred 1-18 part, wherein, cobalt oxide can for 0.1-5 part, it is preferable that 0.15-4 part, ferrous oxide can be 0.1-5 part, preferably 0.5～4 part, iron sesquioxide can be 0.01～10 part, it is preferable that 0.05～8.5 part.
The feeding quantity of corresponding oxidation aluminum may range from 0.1-6 weight portion, it is preferable that 0.5～5.5 weight portion, silicon dioxide feeding quantity may range from 0.1-6 weight portion, it is preferable that 0.5～5.5 weight portion.
It is a further object of the present invention to provide a kind of method preparing 3D magnetic pearlescent pigment, step is as follows:
(1) 100 parts of pearlescent pigments are mixed with deionized water, formed initial solid content be 3-25wt%, preferred 4-20wt%, more preferably between 5-20wt%, such as the suspension of 6%, 8%, 10%, 12%, stir, and by suspension heating to 60～95 DEG C it is preferred that 70-90 DEG C, further preferably 75-85 DEG C；
(2) with aqueous slkali by the pH regulator of suspension to 5.0-10.0, preferred 6.0-9.0, add the mixed liquor of cobalt oxide, ferrous oxide, cobalt salt that ferrum oxide is corresponding, ferrous salt, iron salt (such as adding up to 0.5～15 weight portion), the total weight parts making the cobalt oxide, ferrum oxide and the ferrous oxide that generate is 0.21～20 part, preferably 1～18 part (cobalt oxide: 0.1～5 part, it is preferable that 0.15～4.0 part；Ferrous oxide: 0.1～5 part, it is preferable that 0.5～4.0 part；Ferrum oxide: 0.01～10 part, preferably 0.05～8.5 part), cobalt oxide, ferrous oxide, ferrum oxide the ratio of clad ratio be (1～5): (1～5): (0.1～10), it is preferable that 1:(1～5): (0.5～2.5) is (such as with 1gCoCl2·6H2O is benchmark, corresponding CoCl2·6H2O、FeCl2·4H2O、FeCl3·6H2O feeding quantity scope is: 1.00g:(0.87g～5.05g): (0.52g～2.81g)), keeping pH value constant with aqueous slkali, after reinforced, regulating pH with aqueous slkali is 9.0～11, constant temperature stirring (such as 5 minutes～1 hour, it is preferable that about 15 minutes)；
(3) regulating pH with salt slow acid is 2-5.0, preferred 2.5-4, non-constant pH value, and a mass fraction of dropping is the aluminum salt solution corresponding with aluminium oxide (such as liquor alumini chloridi) of 5%-30%, preferred 8%-25%, and the amount of addition, with Al2O3Meter, for the 0.5wt%～10wt% of base material, constant temperature stirring (such as 5 minutes～1 hour, it is preferable that about 15 minutes) after stopping is reinforced；
(4) slowly regulating pH with aqueous slkali is 5.0-10.0, preferred 6.0-9.0, the a mass fraction of dropping is 5%～30%, the silicate solutions corresponding with silicon dioxide (such as solution of sodium metasilicate through) of preferred 8%-25%, use hydrochloric acid constant pH simultaneously, the amount added, with SiO2Meter, for the 0.5wt%～10wt% of base material, after reinforced end, regulating pH with aqueous slkali is 7.0～11, constant temperature stirring (such as 20 minutes～1 hour, it is preferable that about 35 minutes)；
(5) step (4) is obtained solution be filtered, wash, dry, calcine, obtain the magnetic pearlescent pigment with 3D specially good effect.
The optional sodium hydroxide of alkali in wherein said aqueous slkali, ammonia, sodium carbonate, and/or the solution of their combination in any, for instance aqueous slkali is sodium hydroxide or the aqueous solution of potassium hydroxide or sodium carbonate, such as 5-30% aqueous solution, or the ammonia of 5～30%.
The cobalt salt that described cobalt oxide is corresponding can be CoCl2、Co(NO3)2、CoSO4, and/or the solution of their combination in any.
The ferrous salt that described ferrous oxide is corresponding is selected from FeSO4、FeCl2、FeCO3, and/or the solution of their combination in any.
The iron salt that described ferrum oxide is corresponding is selected from Fe (NO3)3、Fe2(SO4)3、FeCl3, and/or the solution of their combination in any.
The optional AlCl of aluminium salt that described aluminium oxide is corresponding3With Al (NO3)3, and/or the solution of their combination in any.
The silicate that described silicon oxide is corresponding is selected from Na2SiO3、CaMg3Si4O12、Ca3SiO5, and/or the solution of their combination in any.
Drying is such as at 100-120 DEG C, it is preferable that dry 10 minutes～1 hour at about 105 DEG C, it is preferable that about 30 minutes.
Calcining is such as at 670～720 DEG C, it is preferable that calcine 10 minutes～1 hour at about 700 DEG C, it is preferable that about 30 minutes.
It should be noted that, above-mentioned preparation method is prepared using pearlescent pigment as initiation material, but pearlescent pigment can also be prepared as initiation material by the base material such as natural mica, synthetic mica, tabular alumina, lamellar silicon oxide, glass flake, then carrying out step (1)-(5) of the present invention, this is also within the scope of the invention.
Invention additionally provides above-mentioned 3D magnetic pearlescent pigment and can be used for the purposes of printing-ink, printing in textiles, packaging material.
3D magnetic series pearlescent pigment prepared by the present invention utilize surface magnetism material walk magnetic phenomenon can produce solid, illusion 3D effect.The preparation method of the 3D magnetic series pearlescent pigment of the present invention, the difficult problem that the ferrous iron existed in prior art is easily oxidized can be overcome, reduce ferroso-ferric oxide loss, reduce magnetic losses, and the part cobalt acid ferrum of generation is stably not easily oxidized so that the preservation of pigment has chronicity.
Generally speaking, the 3D magnetic series pearlescent pigment of the present invention is the 3D magnetic effect pigment that a kind of technique simplifies, price material benefit is durable, production economy is profitable, magnetic is good.The 3D magnetic series pearlescent pigment of the present invention can apply to the 3D effect of printing-ink, printing in textiles, packaging material etc. and builds, the prospect being widely applied.
Detailed description of the invention
For better illustrating the present invention, below the technical scheme in the embodiment of the present invention being fully described by, following example are used for further illustrating the present invention, but are not intended to the present invention.
In this application, part is weight portion, unless otherwise prescribed.
Embodiment 1
With finished product pearlescent pigment for base material, it is coated with the cobalt oxide of different proportion, ferrous oxide, ferrum oxide.
(1) weighing 100g gram of QC110 silvery white pearlescent pigment (originating from Guangxi seven color pearlescent material joint stock company limited), put in the reactor that volume is 1L, add 800 ml deionized water, stirring is so as to dispersed one-tenth suspension.
(2) this suspension heated in thermostat water bath and stablize at 65 DEG C, with the liquid caustic soda (liquified hydrogen sodium oxide) that mass fraction is 31% by the pH regulator of this suspension to 8.5.
(3) regulating suspension temperature is 75 DEG C, and pH is 9.0.By 10.93gCoCl2·6H2O、409.0mLFeCl3·6H2O (75g/L) and 9.51gFeCl2·4H2O mix and blend makes mixed liquor, drips this mixed liquor with the speed of 0.75ml/min, keeps pH constant with sodium hydroxide solution simultaneously, and after reinforced, being raised by pH is 10, and constant temperature stirs 15 minutes.
(4) adjusting suspension temperature is 75 DEG C, is 3.5 with salt acid for adjusting pH.Dropping 23.67gAlCl3·6H2O solid is dissolved in the aqueous solution of 250mL water, fast drop.Stop reinforced rear constant temperature stirring 15min.
(5) slowly regulating pH with liquid caustic soda is 9.0.Weigh 23.61gNa2SiO3·9H2O solid is dissolved in 250mL water and is configured to solution, drips this mixed liquor with the speed of 0.7ml/min, keeps pH constant with hydrochloric acid simultaneously.After stopping is reinforced, regulating pH with liquid caustic soda is 11, and constant temperature stirs 35 minutes.
(6) reacted rear suspension liquid through filtering, with deionized water wash, dried 30 minutes at 105 DEG C.
(7) calcining 30 minutes at 700 DEG C, discharging naturally cools to room temperature, and washing and drying obtains silvery white magnetic pearlescent pigment again.
Gained sample clad ratio: Conjugate ferrite 15%,
Wherein CoO%=3.33%, FeO%=3.33%, Fe2O3%=8.34%；
Al2O3%=5%,
SiO2%=5%.
Embodiment 2
With finished product pearlescent pigment for base material, it is coated with the cobalt oxide of different proportion, ferrous oxide, ferrum oxide.
(1) weighing 100g gram of QC303 imperial family gold finished product pearlescent pigment, put in the reactor that volume is 1L, add 800 ml deionized water, stirring is so as to dispersed one-tenth suspension.
(2) being heated in thermostat water bath by this suspension and stablize at 65 DEG C, the liquid caustic soda with 31% is by the pH regulator of this suspension to 8.5.
(3) regulating suspension temperature is 75 DEG C, and pH is 9.0.By 4.833gCoCl2·6H2O、87.2mLFeCl3·6H2O (75g/L) and 10.311gFeCl2·4H2O mix and blend is configured to mixed liquor, drips this mixed liquor with the speed of 0.5ml/min, keeps pH constant with sodium hydrate aqueous solution simultaneously, and after reinforced, rising pH is 10, and constant temperature stirs 15 minutes.
(4) adjusting suspension temperature is 75 DEG C, is 3.5 with salt acid for adjusting pH.Dropping 11.84gAlCl3·6H2O solid is dissolved in the aqueous solution of 110mL water, fast drop, and pH is non-constant.Stop reinforced rear constant temperature stirring 15min.
(5) slowly regulating pH with liquid caustic soda is 9.0.Weigh 11.80gNa2SiO3·9H2O solid is dissolved in 110mL water and is configured to solution, drips this mixed liquor with the speed of 0.7ml/min, keeps pH constant with hydrochloric acid simultaneously.After stopping is reinforced, regulating pH with liquid caustic soda is 11, and constant temperature stirs 35 minutes.
(6) reacted rear suspension liquid through filtering, with deionized water wash, dried 20 minutes at 105 DEG C.
(7) calcining 30 minutes at 700 DEG C, discharging naturally cools to room temperature, and washing and drying obtains golden magnetic pearlescent pigment again.
Gained sample clad ratio: Conjugate ferrite 7%,
Wherein CoO%=1.5%, FeO%=3.6%, Fe2O3%=1.9%；
Al2O3%=2.5%,
SiO2%=2.5%.
Embodiment 3
With finished product pearlescent pigment for base material, it is coated with the cobalt oxide of different proportion, ferrous oxide, ferrum oxide.
(1) weighing 100g gram of QC193 silvery white pearlescent pigment, put in the reactor that volume is 1L, add 800 ml deionized water, stirring is so as to dispersed one-tenth suspension.
(2) being heated in thermostat water bath by this suspension and stablize at 65 DEG C, the liquid caustic soda with 31% is by the pH regulator of this suspension to 8.5.
(3) regulating suspension temperature is 75 DEG C, and pH is 9.0.By 0.51gCoCl2·6H2O、4.5mLFeCl3·6H2O (60g/L) and 2.12gFeCl2·4H2O mixes and is diluted with water to 10ml, drips this mixed liquor with the speed of 0.4ml/min, keeps pH constant with sodium hydrate aqueous solution simultaneously, and after reinforced, rising pH is 10, and constant temperature stirs 15 minutes.
(4) adjusting suspension temperature is 75 DEG C, is 3.5 with salt acid for adjusting pH.Dropping 2.37gAlCl3·6H2O solid is dissolved in the aqueous solution of 25mL water, fast drop, and pH is non-constant.Stop reinforced rear constant temperature stirring 15min.
(5) slowly regulating pH with liquid caustic soda is 9.0.Weigh 2.36gNa2SiO3·9H2O solid is dissolved in 25mL water and is configured to solution, drips with the speed of 0.4ml/min, keeps pH constant with hydrochloric acid.After stopping is reinforced, regulating pH with liquid caustic soda is 11, and constant temperature stirs 35 minutes.
(6) reacted rear suspension liquid through filtering, with deionized water wash, dried 15 minutes at 105 DEG C.
(7) calcining 30 minutes at 700 DEG C, discharging naturally cools to room temperature, and washing and drying obtains silvery white magnetic pearlescent pigment again.
Gained sample clad ratio: Conjugate ferrite 1%,
Wherein CoO%=0.16%, FeO%=0.76%, Fe2O3%=0.08%；
Al2O3%=0.5%,
SiO2%=0.5%.
Comparative example 1
Method disclosed in CN102766357A in patent, 50gQC110 silvery white pearlescent pigment (Guangxi seven color pearlescent material joint stock company limited) and suitable quantity of water are poured in 1000ml there-necked flask, add water to 600ml graduation position, then stirring makes pearlescent pigment make it dispersed, it is warming up to 80 DEG C, keeps this temperature.In there-necked flask, it is filled with nitrogen, the air in displacement there-necked flask with the speed of 0.2L/ minute.Then in a nitrogen atmosphere, adding 20mL concentration is the solution of ferrous chloride of 300g/L, and adds sodium hydroxide solution adjustment pH to 6.Dropping 23.6mL concentration is 30g/L potassium chlorate solution, and potassium chlorate will part Fe2+It is oxidized to Fe3+, question response cools down after terminating.Vacuum filtration also uses deionized water flush cake, is again put into by filter cake and adds water to 700mL liquid level in 1000mL beaker, stirs evenly, and adjusts and is warming up to 80 DEG C.It is slowly added dropwise 165mL sodium silicate solution (in silicon dioxide, mass content 10%) and 27.5mL liquor alumini chloridi (with AlCl3Meter, mass content 10%), stirring also maintains with the hydrochloric acid of 5% and regulates pH to 7, after stirring half an hour, sucking filtration by deionized water flush cake 6 times.Dry at 105 DEG C after filter cake in above step is drained, then calcine 30 minutes at 560 DEG C in a nitrogen atmosphere, obtain finished product.After gained finished product pearlescent pigment preserves 6 months, magnetic substantially reduces, it does not have produce three-dimensional, dreamlike 3D effect.
Embodiment result such as following table:
Claims (14)
1. a magnetic pearlescent pigment with 3D effect; it includes pearlescent pigment, the magnetic clad being made up of cobalt oxide, ferrum oxide and ferrous oxide on pearlescent pigment layer, the protective layer on magnetic clad, and wherein pearlescent pigment includes base material and one or more layers pearlescent pigment layer；
Wherein, the ratio of the clad ratio of cobalt oxide, ferrous oxide, ferrum oxide is (1 ~ 5): (1 ~ 5): (0.1 ~ 10).
2. the magnetic pearlescent pigment with 3D effect according to claim 1, wherein, cobalt oxide, ferrous oxide, ferrum oxide the ratio of clad ratio be 1:(1 ~ 5): (0.5 ~ 2.5).
3. the magnetic pearlescent pigment with 3D effect according to claim 1, wherein, the weight ratio of the described 3D stereoeffect each component of series of magnetic pearlescent pigment is:
Pearlescent pigment 100 parts,
Cobalt oxide+ferrum oxide+ferrous oxide 0.21 ~ 20 part,
Aluminium oxide 0.1 ~ 6 part,
Silicon oxide 0.1 ~ 6 part,
Cobalt oxide 0.1 ~ 5 part,
Ferrous oxide 0.1 ~ 5 part,
Ferrum oxide 0.01 ~ 10 part.
4. the magnetic pearlescent pigment with 3D effect according to claim 3, wherein, the weight ratio of the described 3D stereoeffect each component of series of magnetic pearlescent pigment is:
Pearlescent pigment 100 parts,
Cobalt oxide+ferrum oxide+ferrous oxide 1 ~ 18 part,
Aluminium oxide 0.5 ~ 5.5 part,
Silicon oxide 0.5 ~ 5.5 part,
Cobalt oxide 0.15 ~ 4.0 part,
Ferrous oxide 0.5 ~ 4.0 part,
Ferrum oxide 0.05 ~ 8.5 part.
5. the magnetic pearlescent pigment with 3D effect according to any one of claim 1-4, wherein, pearlescent pigment is natural mica, synthetic mica, tabular alumina, lamellar silicon oxide, glass flake substrate material cladding SnO2、TiO2、SiO2And Fe2O3In the obtained pearlescent pigment of one or more rete.
6. the magnetic pearlescent pigment with 3D effect according to claim 5, wherein, pearlescent pigment is selected from: base material+TiO2Layer, base material+SnO2Layer+TiO2Layer, base material+SnO2Layer+TiO2Layer+SiO2Layer+TiO2Layer, base material+SnO2Layer+TiO2Layer+SiO2Layer+SnO2Layer+TiO2Layer, base material+TiO2Layer+Fe2O3Layer, base material+TiO2Layer+SiO2Layer+Fe2O3Layer, base material+TiO2Layer/Fe2O3Layer, base material+TiO2Layer/Fe2O3Layer+SiO2Layer+TiO2Layer/Fe2O3Layer, base material+Fe2O3Layer, base material+Fe2O3Layer+TiO2Layer, base material+Fe2O3Layer+SiO2Layer+Fe2O3Layer, base material+TiO2Layer+SiO2Layer+TiO2Layer in one or more.
7. the magnetic pearlescent pigment with 3D effect according to any one of claim 1-4, wherein, described protective layer is SiO2、MgO、Al2O3、MgF2、AlF3And their combination in any.
8. the magnetic pearlescent pigment with 3D effect according to claim 7, wherein, described protective layer is SiO2Or Al2O3Layer.
9. the magnetic pearlescent pigment with 3D effect according to claim 7, wherein, protective layer includes the alumina layer on magnetic clad and the silicon dioxide layer on alumina layer.
10. the preparation method of the magnetic pearlescent pigment with 3D effect according to any one of claim 1-9, comprises the steps:
Being mixed with deionized water by 100 weight portion pearlescent pigments, forming initial solid content is the suspension of 3-25wt%, stirs, and heats suspension to 60 ~ 95 DEG C；
With aqueous slkali by the pH regulator of suspension to 5.0-10.0, add the mixed liquor of cobalt oxide, ferrous oxide, cobalt salt that ferrum oxide is corresponding, ferrous salt, iron salt, make to be calculated as 0.21 ~ 20 weight portion by the summation of cobalt oxide, ferrum oxide and ferrous oxide, cobalt oxide, ferrous oxide, ferrum oxide the ratio of clad ratio be (1 ~ 5): (1 ~ 5): (0.1 ~ 10), keep pH value constant with aqueous slkali, after reinforced, regulating pH with aqueous slkali is 9.0 ~ 11, and constant temperature stirs；
Regulating pH with salt slow acid is 2-5.0, non-constant pH value, and a mass fraction of dropping is the aluminum salt solution corresponding with aluminium oxide of 5%-30%, and the amount of addition, with Al2O3Meter, for the 0.5% ~ 10% of base material, stops reinforced rear constant temperature stirring；
Slowly regulating pH with aqueous slkali is 5.0-10.0, and a mass fraction of dropping is the silicate solutions corresponding with silicon dioxide of 5% ~ 30%, uses hydrochloric acid constant pH simultaneously, and the amount of addition, with SiO2Meter, for the 0.5% ~ 10% of base material, after reinforced end, regulating pH with aqueous slkali is 7.0 ~ 11, and constant temperature stirs；
Step (4) is obtained solution be filtered, wash, dry, calcine, obtain the magnetic pearlescent pigment with 3D specially good effect.
11. preparation method according to claim 10, wherein, in step (1), forming initial solid content is the suspension of 5-20wt%；In step (2), with aqueous slkali by the pH regulator of suspension to 6.0-9.0；In step (3), regulating pH with salt slow acid is 2.5-4.0；In step (4), slowly regulating pH with aqueous slkali is 6.0-9.0.
12. preparation method according to claim 10, the alkali in wherein said aqueous slkali is selected from sodium hydroxide, ammonia, sodium carbonate and/or the aqueous solution of their combination in any.
13. the preparation method according to claim 10 or 11, wherein, the cobalt salt that described cobalt oxide is corresponding is selected from CoCl2、Co(NO3)2、CoSO4, and/or the solution of their combination in any；And/or
The ferrous salt that described ferrous oxide is corresponding is selected from FeSO4、FeCl2、FeCO3, and/or the solution of their combination in any；And/or
The iron salt that described ferrum oxide is corresponding is selected from Fe (NO3)3、Fe2(SO4)3、FeCl3, and/or the solution of their combination in any；And/or
The aluminium salt that described aluminium oxide is corresponding is selected from AlCl3With Al (NO3)3, and/or the solution of their combination in any；And/or
The silicate that described silicon oxide is corresponding is selected from Na2SiO3、CaMg3Si4O12、Ca3SiO5, and/or the solution of their combination in any.
14. the magnetic pearlescent pigment with 3D effect according to any one of claim 1-9 or by the magnetic pearlescent pigment with 3D effect prepared by preparation method according to any one of claim 10-13 for printing-ink, printing in textiles, packaging material purposes.
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| CN104893366B (en) * | 2015-06-18 | 2016-07-06 | 广西七色珠光材料股份有限公司 | A kind of magnetic pearlescent pigment with 3D effect and preparation method thereof |
| CN105086524A (en) * | 2015-09-15 | 2015-11-25 | 广西七色珠光材料股份有限公司 | Black nacreous pigment and preparation method thereof |
| CN106807939A (en) * | 2015-11-27 | 2017-06-09 | 上海朗亿功能材料有限公司 | One type of metal flakelike powder |
| CN105385193A (en) * | 2015-12-07 | 2016-03-09 | 李学英 | Inducible filtering pigment piece 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 |
| CN108752978B (en) * | 2018-07-10 | 2020-05-08 | 福建坤彩材料科技股份有限公司 | Green-phase golden pearlescent pigment based on synthetic mica and preparation method and application thereof |
| EP3783069B1 (en) * | 2019-08-19 | 2021-12-15 | Technische Universität Berlin | Composition containing 3d-shaped metal effect pigments, and method for producing said pigments |
| CN110713736A (en) * | 2019-10-31 | 2020-01-21 | 南阳市凌宝珠光颜料有限公司 | Preparation method of color magnetic bead optical pigment |
| CN111171602B (en) * | 2019-12-30 | 2022-05-10 | 河北欧克新型材料股份有限公司 | Preparation method of pearlescent pigment |
| CN112708288A (en) * | 2020-05-21 | 2021-04-27 | 厦门大学 | Magnetic structure color film |
| CN113527914B (en) * | 2021-07-22 | 2022-05-27 | 浙江瑞成新材料股份有限公司 | Magnetic pearlescent pigment and preparation method thereof |
| CN114276700A (en) * | 2022-01-06 | 2022-04-05 | 广西七色珠光材料股份有限公司 | Titanium-free golden pearlescent pigment and preparation method and application thereof |
| CN114716847B (en) * | 2022-05-23 | 2023-08-01 | 贵阳职业技术学院 | Preparation method of pearlescent pigment with flaky alpha-alumina as matrix |
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| US6139615A (en) * | 1998-02-27 | 2000-10-31 | Engelhard Corporation | Pearlescent pigments containing ferrites |
| WO2008011616A2 (en) * | 2006-07-21 | 2008-01-24 | Basf Corporation | Synthetic mica based pearlescent pigments containing ferrites |
| US7850775B2 (en) * | 2006-11-09 | 2010-12-14 | Sun Chemical Corporation | Multi-colored lustrous pearlescent pigments |
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| DE102009037932A1 (en) * | 2009-08-19 | 2011-02-24 | Eckart Gmbh | High gloss multi-layer pearlescent pigments with narrow size distribution and process for their preparation |
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| CN102766357A (en) * | 2012-08-10 | 2012-11-07 | 杭州弗沃德精细化工有限公司 | Method for preparing magnetic permeability pearlescent pigment |
| EP2799397B1 (en) * | 2013-04-30 | 2018-06-20 | Merck Patent GmbH | alpha-Alumina flakes |
| CN103602102A (en) * | 2013-11-15 | 2014-02-26 | 浙江凯色丽科技发展有限公司 | 3D (Three-Dimensional) color-changing shimmer pigment |
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Denomination of invention: A magnetic pearlescent pigment with 3D effect and its preparation method Effective date of registration: 20230928 Granted publication date: 20160706 Pledgee: China Everbright Bank Co.,Ltd. Liuzhou Branch Pledgor: GUANGXI CHESIR PEARL MATERIAL Co.,Ltd. Registration number: Y2023450000126 |