CN101189306A - Sparkle effect of unique particle size distribution - Google Patents
Sparkle effect of unique particle size distribution Download PDFInfo
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- CN101189306A CN101189306A CNA2006800195427A CN200680019542A CN101189306A CN 101189306 A CN101189306 A CN 101189306A CN A2006800195427 A CNA2006800195427 A CN A2006800195427A CN 200680019542 A CN200680019542 A CN 200680019542A CN 101189306 A CN101189306 A CN 101189306A
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- glass
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- effect pigment
- oxide
- pigment
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- 230000000694 effects Effects 0.000 title claims abstract description 35
- 238000009826 distribution Methods 0.000 title claims description 19
- 239000002245 particle Substances 0.000 title abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 99
- 239000000049 pigment Substances 0.000 claims abstract description 62
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 51
- 229910044991 metal oxide Inorganic materials 0.000 claims description 36
- 150000004706 metal oxides Chemical class 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 241001005836 Euchloe ausonia Species 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000002537 cosmetic Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000006911 nucleation Effects 0.000 description 13
- 238000010899 nucleation Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- -1 metal oxide compound Chemical class 0.000 description 6
- 239000010445 mica Substances 0.000 description 6
- 229910052618 mica group Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000001066 destructive effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000003608 titanium Chemical class 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001251094 Formica Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000062730 Melissa officinalis Species 0.000 description 1
- 235000010654 Melissa officinalis Nutrition 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010040829 Skin discolouration Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000008257 shaving cream Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
An effect pigment formed from a synthetic platelet substrate such as glass flake has improved sparkle by reducing the amount of substrate particles having a size of less than 9 microns and greater than 85 microns. The present effect pigment is useful in cosmetics, personal care products, and industrial applications such as automotive paints.
Description
Unsettled 60/667276 right that the application requires to submit on April 1st, 2005, this article is fully incorporated in this.
The field
The distribution of sizes that the present invention relates to the matrix by changing effect pigment is improved the optical property of synthetic effect pigment.
Background
Give nacreous lustre, metalluster and/or can realize by pearliness or pearly pigment that use comprise the thin layer platelet of metal oxide-coated near the many color effects of iridescent.These pigment are at first at United States Patent (USP) 3,087, describe in 828 and 3,087,829, and its property description can be at PigmentHandbook, Vol.1, Second Edition, pp 829-858, John Wiley ﹠amp; Sons finds among the N.Y.1988.
These oxide compounds are deposited on the surface of thin layer platelet with the form of thin layer.The most frequently used oxide compound is a titanium dioxide at present.Second commonly used be ferric oxide, other available oxide compounds comprise the oxide compound of tin, chromium, zirconium and the combination or the mixture of oxide compound.
In order to obtain best pearlescent appearance, the coating of the metal oxide on the thin layer platelet must be smooth and uniform.If the formation irregular surface scattering of light takes place, and coated thin layer platelet can not be re-used as pearly pigment.The also necessary strong adhesion of coating of metal oxides is on the thin layer platelet, otherwise coating is separated with work in-process, and considerable glossy destroys and loss thereby produce.
In the process of the coating on these thin layer platelets of preparation, may form not attached to the particle on the thin layer platelet.These small-particles produce scattering of light, and make pigment opaque.If there is too many small-particle, may reduce or lose pearlescent appearance.Adding these coating of metal oxides to the thin layer platelet can be difficult to keep gloss, color and color homogeneity, and up to now, the flake substrate of the significant application of commercial acquisition only limits to mica.
Advised using other multiple flaky materials as matrix to form these pearly pigments.These comprise insoluble inorganic materials, for example glass, enamel, potter's clay, porcelain or other siliceous substances, the surface of metal object and organic polymer (as polycarbonate) material.Referring to for example United States Patent (USP) 3,123,485,3,219,734,6,616,100,3,444,987,4,552,593 and 4,735,869.Although for example mentioned glass as a kind of possibility in the United States Patent (USP) 3,331,699 in many occasions, the commodity pearly-lustre product that uses glass to make is mainly used in cosmetic use, and wherein big relatively flass platelet matrix is coated.
Above-mentioned United States Patent (USP) 3,331, disclose the particulate semitransparent layer coated glass thin slice that can use the metal oxide (for example titanium dioxide) with high refractive index in 699, prerequisite is at first to deposit on the glass flake at undissolved nucleation material from the acid solution of the semitransparent layer of depositing metal oxide wherein.Wherein the thickness of disclosed glass flake is the order of magnitude of 1.0-5.0 micron, and the major dimension size from about 10 microns to about 400 microns variations, wherein at least 50% below 75 microns, and at least about 85% below 150 microns.The embodiment of this patent has illustrated following glass flake distribution of sizes.
| Sieve | Size (micron) | Weight % |
| The 40-100 order | The 149-420 micron | 12.9 |
| The 100-200 order | The 74-149 micron | 32.5 |
| The 200-325 order | The 44-74 micron | 22.0 |
| The 325-400 order | The 37-44 micron | 9.6 |
| To 400 orders | Less than 37 microns | 23.0 |
United States Patent (USP) 5,436,077 has illustrated and has had metal cladding the glass flake substrate of (forming for example densification protection tectum of titanium dioxide of metal oxide on it).In this patent, the character of glass is unessential, because metallic coating provides desirable outward appearance and exist the seal coat of metal oxide not influenced by corrosive atmosphere with the protection metal level.Disclose with silvering and also applied SiO subsequently
2The example of the glass flake that the mean diameter of layer is 15 microns.
Be transferred to the coating that discloses, even metal oxide compound slick in same transferee's the United States Patent (USP) 6,045,914 in preparation on the glass flake, its attached to glass flake on to produce the method for high-quality pearlescent pigment.According to disclosed method wherein, form pearly pigment by the thin slice that contains water film and calcining coating subsequently of on glass flake, setting up titanium and/or ferriferous oxide, its prerequisite is that employed glass flake is the C glass flake, and when the waterbearing stratum was titanium, this process was rutilization (rutilizing) process.This article discloses has similar TiO
2And Fe
2O
3The size and dimension of the mica thin layer platelet that uses in the coated mica pearly pigment, and have the glass flake of the thickness of the average particle size particle size of about 1-250 micron and about 0.1-10 micron thus.Can use more to be cubical thin slice with thickness of similar particle size and about 10-100 micron, still, because low length-to-diameter ratio, pearl effect significantly reduces.Yet in all embodiments, pigment is made by 100 microns of mean diameters or bigger glass flake.By reference with US 6,045,914 are incorporated into this in full.
Synthetic thin layer platelet for example the production of glass flake often to cause with the Gaussian curve be the distribution of sizes of thin layer platelet of feature.Sign is by limiting along the thin layer platelet size of the thin layer platelet of the minimum 10 volume % of Gaussian curve, 50 volume % and 90 volume % as the useful especially method of the distribution of sizes of the synthetic thin-layer tablet eutectic substance of the matrix production of effect pigment and use.This classification can be known as D10, D50 and the D90 value of thin layer platelet distribution of sizes.Thus, the flake substrate particle that refers to 10 volume % of the matrix with D10 of a certain size has high size to this value.For example, this transferee has many based on the micaceous effect pigment on market, especially for makeup and car paint purposes.Comprising LUMINA
Mica-based effect pigment, its D10 are 10 microns, and D50 is 22 microns, and D90 is 45 microns.Thus, LUMINA
The mica-based effect pigment can be described below: the mica thin layer platelet of 10 volume % has extremely high and comprises 10 microns size, the thin layer platelet of 50 volume % have high to and comprise 22 microns size, the thin layer platelet of 90 volume % have high to and comprise 45 microns size.
But, as previously mentioned, have quite much bigger size based on the effect pigment of glass flake.This is reflected on the distribution of sizes.Thus, this transferee and Nippon Sheet Glass are with based on REFLECKS
TMAnd FIREMIST
The trade(brand)name of pigment sell pigment based on glass flake, the former D10 is 17 microns, the former is 45 microns for D50, latter D10 is 50 microns, D50 is for being 100 microns.These pigment have king-sized size and can not be used for automobile pigment effectively, because pigment itself often highlights from the paint film of using, thereby the optical property of film are had a negative impact.In addition, big pigment can not be easily by through being usually used in the spraying equipment of applied coatings.Other based on the pigment of glass for example by Merck with RONASTAR
The pigment of selling also has large size, and its D10 is higher than 30, and D50 is higher than 65.
In order to produce operable effect pigment in the car paint by glass flake, Nippon SheetGlass has developed a kind of glass flake substrate with the remarkable less distribution of sizes that formed than the past.The D10 of this product is 8 microns, and D50 is 20 microns, and D90 is 37 microns.But, do not have evidence to show and successfully used TiO
2Coating is used for the effect pigment of car paint with production, because the paint film that is formed by pigment lacks gloss, color depth and flash of light.
General introduction
According to the present invention, by particle size distribution be at least 9.5 microns of D10, D50 about 20 microns to surpassing 35 microns less than 40 microns, D90 to less than 85 microns thin layer platelet matrix, the effect pigment that comprises the synthetic thin layer platelet matrix that scribbles translucent (translucent) coating of metal oxides on it is provided.
Have been found that, the effect pigment of being produced by the synthetic thin layer platelet matrix through applying with desirable distribution of sizes can be used for all types of compositions and comprises plastics, makeup and particularly car paint, and do not have the problem of the obstruction paint spray equipment of prior art, and there be not disadvantageous big outstanding (this for effect pigment by the synthetic thin-layer tablet brilliant prior art that form be serious problems) of thin layer platelet on paint film.On the other hand, make short grained amount reduce to minimum to reduce the particulate light scattering effect of minimum size.
Surprisingly, have been found that by making D10 be increased to 9.5 microns from 8 microns that the flash effect of the film that is obtained by pigment has obtained remarkable improvement at least.Under the high-caliber gloss of film and reflectivity, observe the flash of light of improvement that can visual perception.
Detailed Description Of The Invention
According to the present invention, form pearly pigment by the thin-layer tablet crystalline substance that contains water film and calcine subsequently of on synthetic thin layer platelet matrix, setting up metal oxide through applying.The present invention be more particularly directed to form pearly pigment from synthetic thin layer platelet matrix, the distribute pigment that makes formation can be used for multiple product for example colored plastic, makeup and especially for car paint thereby described matrix has specific dimensions.The synthetic thin layer platelet that is used to form pearly pigment of the present invention comprises, for example, and aluminum oxide, silicon-dioxide, Bismuth Oxychloride, boron nitride and glass.Glass flake is significant especially for the present invention.
The synthetic thin layer platelet matrix that is used for purpose of the present invention for example glass flake substrate is the particle of glass for example, and it has the two-dimension sizes (length and width) that is far longer than the third dimension on similarity number magnitude and the characteristic.Conduct of the present invention is used on the size distribution character of the useful thin layer platelet of the matrix of coating of metal oxides has Gaussian distribution substantially, wherein the volume size score distribution is as follows: D10 is at least 0.95 micron, D50 is about 20 to less than 40 microns, and D90 is to less than 85 microns more than 35.The thin layer platelet that this distribution of sizes refers at least 10 volume % have high to and comprise at least 9.5 microns size, the flass platelet of at least 50 volume % have high to and comprise 20 to less than 40 microns size, the flass platelet of at least 90 volume % have high to and comprise 35 to size less than 85 microns.Have been found that the pigment that obtains is not meticulous more by changing D10 from 8 at least 9.5 microns, this has a negative impact with scattered light and to the flash of light of the film that formed by pigment.General size distributes will meet Gaussian distribution, and particle is of a size of about 1 to about 150 microns at the unidimensional of maximum.The thickness that generally includes the synthetic thin layer platelet of glass flake is about below 0.1 to 5 micron.Desirable size and distribution of sizes can be by suitably carrying out classification to thin slice, for example obtain by selected screen sizing etc.
Although the present invention relates to the synthetic thin layer platelet of any kind, glass flake is useful especially.The character of glass is not critical.For many purposes, desirable is transparent, colourless glass flake, can comprise by comprising that in melt selected chemical is endowed the special glass of the glass of color but also can use.
Glass flake is desired in the industry, because their unusual rubber-likes and also can be attractive on the optics.Glass is mainly by SiO
2And Al
2O
3Constitute and also can comprise ZnO, CaO, B
2O
3, Na
2O and K
2O and FeO and Fe
2O
3Glass flake be by stretching fused glass to thin plate, ball or Glass tubing, subsequently glass being crushed to thin slice prepares.Can prepare big hollow ball, solidify then and crush and other slice production methods.Glass can be divided into A glass, C glass or E glass.A glass is soda-lime silicate glass, and is generally used for producing window.Compare with potassium, A glass contains more sodium and contains calcium oxide.C glass is also referred to as chemical glass, is acidproof and glass humidity corrosion.C glass often contains zinc oxide and makes more other oxide compounds of chemically-resistant destructive of thin slice.E glass or electrical glass hint as its title, at the electronic application design, although and at high temperature highly stable, it can be responsive to chemical attack.Following table 1 has shown the composition of several commodity samples of A, C and E glass, by weight percentage.Can see that C glass and A and C glass alter a great deal on chemical constitution, and in fact the composition of A and E glass can be very similar with C glass.
Table 1
| Type | A glass | C glass | C glass | E glass | E glass |
| SiO 2 | 72.5 | 65-70 | 65％ | 52-56 | 52.5 |
| Al 2O 3 | 0.4 | 2-6 | 4％ | 12-16 | 14.5 |
| CaO | 9.8 | 4-9 | 14％ | 20-25 | 22.5 |
| MgO | 3.3 | 0-5 | 3％ | 0-5 | 1.2 |
| B 2O 3 | 0.0 | 2-7 | 5.5％ | 5-10 | 8.6 |
| Na 2O+K 2O | 5.8 | 9-13 | 8.5％ | ＜0.8 | ＜0.5 |
| ZnO | -- | 1-6 | 0 | -- | -- |
| FeO/Fe 2O 3 | 0.2 | -- | 0 | -- | 0.2 |
When enforcement is of the present invention, preferred C or chemotype glass.Although can prepare the coating of metal oxides of A or E glass, the quality product of the pigment that obtains is not as C glass, so commercial value is limited.As preparation TiO
2During coated product, can carry out anatase octahedrite or rutile crystal modification.As the TiO that uses rutile form
2The time, obtain extra best best and the most stable pearly pigment.In addition, employed glass can influence the crystalline form of coating of titanium dioxide.For example, when using common E glass, resulting crystal mainly is anatase octahedrite mutually.In order to obtain rutile, necessary use can be with TiO
2Guide the additive of rutile modification into.
Useful rutile directed agents (director) for example tin is disclosed in the United States Patent (USP) 4,038,099 and 5,433,779 that is transferred to same transferee, and above-mentioned document quotes in full in this.If hope applies this synthetic thin layer platelet with titanium dioxide and wishes rutile titanium dioxide, the rutile directed agents is positioned near the titanium dioxide.Other layers may reside between glass and the rutile directed agents/rutile titanium dioxide.
On glass flake, form thin outer and material that give its needed pearly-lustre characteristic and interference color and be high refractive index semi-transparent metals oxide compound through selecting.The translucent compound of this layer can be colourless or colored and therefore can be by means of providing color from the photoabsorption of colored compound own with by means of the interference color from the thin transparent layer with high refractive index.Be applicable to that preferred semi-transparent metals oxide compound of the present invention is titanium dioxide and ferric oxide.On the other hand, other representative metal oxide that the employing similar fashion works when independent the use comprises the oxide compound and the moisture form thereof of zirconium, chromium, nickel, cobalt, tin.
Adopt the metal oxide coated glass thin slice to carry out according to known method in the micaceous field that forms coating of metal oxides usually.
Usually, described method comprises and disperses the glass flake particle and the precursor of the oxidizing aqueous titanium of formation on dispersion and the thin slice or other metal oxide film coating is mixed.For example, the oxide compound of iron and zirconium separately or add that titania coating is useful coating.
In coating procedure, glass flake is dispersed in the preferred distilled water.The concentration of glass flake in water can be about 5%-30%, although usually preferred concentration is about 10%-20%.
Be dispersed in glass in the water and after placing proper container, adding suitable titanium or other metal source material.In the process of adding titanium or other metal by use suitable alkali for example sodium hydroxide make the pH of resulting dispersion remain on proper level so that moisture titanium dioxide or moisture metal oxide produce precipitation on glass flake.Aqueous acid for example hydrochloric acid can be used for regulating pH.If desired, the thin slice that applies can be washed before being sintered into final pearly pigment and drying.
Although can use other source known in the art similarly, the source of titanium is preferably titanium tetrachloride.Although can use any other iron source known in the art, the source of iron is preferably iron(ic) chloride.If desired, but the coating of sequential aggradation titanium and iron.Method is well known in the art.For example, refer again to aforementioned US patent 3,331,699, at this it is introduced in full with for referencial use, found now glass flake can adopt have high refractive index metal oxide for example the particulate semitransparent layer of zirconium dioxide, chromic oxide etc., particularly titanium dioxide or hydrated titanium dioxide and ferric oxide apply, condition is at first to deposit the nucleation surface that comprises very trickle metal oxide powder on glass flake, and above-mentioned metal oxide powder is insoluble to the acidic solution that is deposited the semitransparent layer of described metal oxide by it.Resulting product is the pearly-lustre flaky pigment, and this pigment demonstrates glossiness flash of light of height and the bright color that the variation with metal oxide semitransparent layer thickness changes.
According to US patent 3,331,699 method, the pearly-lustre flaky pigment comprises three kinds of components: 1) glass flake substrate, 2) be deposited on sour insoluble petal oxide compound on the glass flake, forming acceptable nucleation surface and 3 for the layer of deposition semi-transparent metals oxide particle on the described glass flake) the thin semitransparent layer of the metal oxide of sedimentary low particle size on sour insoluble petal oxide surface through selecting.
Under any circumstance, subsequently with in the treated glass flake water in suspension, Xiang Shuizhong adds for example strong acid solution of titanyl sulfate of titanium salt.Heated mixt makes titanium salt be hydrolyzed into moisture titanium dioxide, described moisture titanium dioxide immediately and selective deposition on treated glass flake.The amount that is deposited on the moisture titanium dioxide on the thin slice can be by the proportional increase of amount of adding the titanium salt liquid in the hydrolysis slurry to and by proportional increase heat-up time.Along with the carrying out of said process, can become gold from initial silvery appearance by observing interference color subsequently, and gradually become redness, purple, blueness and green and follow the tracks of the thickness of outer field moisture titanium dioxide semitransparent layer.By the amount of the used titanium salt of suitable selection, can easily obtain any required interference color.
The optical principle of explaining interference color is known and at many physioptial textbooks Physical Optics of Robert W.Wood for example, third edition, and New York discusses in 1936 the 198th pages.Briefly, interference is the optical phenomena that interrelates from the film surface reflection with light, and wherein the intensity of some wavelength of incident light reduces (destructive interference (restructive interference)) and other wavelength enhancing (constructive interference (constructive interference)).The degree that influences specific wavelength depends on the thickness and the refractive index thereof of film.When thickness makes from the light of a surface reflection of film and the light that passes film and come out from another surface reflection homophase not, then there is destructive interference.
Owing to, therefore when effectively light path (thickness multiply by the twice of refractive index) is a wavelength or simple many times of wavelength in the film of high refractive index, satisfy the condition of maximum destructive interference (minimal reflection) when there is phase reversal in light from the dielectric surface reflex time than high refractive index.Consider the refractive index of film, N, its thickness (t) is given by the following formula with any wavelength X for destructive interference:
t＝nλ/2N
Wherein n is not more than 5 little integer usually.
For identical reasoning,, then there are reflection enhancement or reflection maximum if two kinds of light in mutually, occur.Suppose phase reversal once more, satisfy this condition when effective light path is half wavelength or its odd-multiple, the formula at the maximum reflection place for thickness is:
t＝(n+1/2)λ/2N
Wherein n is 0 or is not more than 5 little integer usually.
When n greater than 1 the time, usually interference is called high-order, second order, three rank or the like.
According to the above, pearly pigment composition of the present invention as can be seen prepares by the colloidal suspension furnishing slurry that glass flake is adopted suitable metal oxide in water medium, described thus metal oxide as the nucleation surface deposition on the glass flake and insoluble in acidic solution by the semitransparent layer of depositing metal oxide wherein.Metal oxide on the glass flake is by heating and/or stir the water medium contain glass flake and become and do not dissolve.Treated subsequently glass flake is for by metal, and for example to have the skin of the semi-transparent metals oxide compound of high refractive index be acceptable to the salts solution of titanium, zirconium, chromium, iron, nickel, tin or cobalt deposition.
The amount that needs sedimentary metal oxide as nucleation surface is seemingly crucial to a certain extent for optimum, although employed optimum quantity is different for different useful reagent.The minimum amount of metal oxide is at least about 0.2% metal oxide based on the weight of glass flake.When using stannic oxide, preferred amount is 0.5%-2%, but can use much bigger amount, be up to 35% or or even 50%, by weight, quality is lost when higher level.Use moisture TiO
2As nucleation when surface, optimum quantity be positioned at above-mentioned scope than lower part, i.e. 0.4%-1%, preferred 0.4%-0.5%, by weight.The optimum quantity of fibrous alumina also above-mentioned scope than lower part, 1%-5% for example, by weight.
For most of purpose, the preferred and the most general metal oxide that forms the nucleation surface is a tin-oxide.For simplicity, be seen as stannic oxide (SnO
2), but its definite character the unknown, so called after " tin-oxide ".It probably at first is converted into oxide compound as moisture oxygen-salt (for example oxygen-muriate) precipitation and in the step of dissolving not in a large number.Various pink salts can be used as the source of tin-oxide and stannous salt and tetravalence pink salt and all are suitable for.The feature of many pink salts is height colloidal suspensoids of solution easy hydrolysis when dilution formation positively charged.It seems that the visible trend of above-mentioned formation colloidal suspension be to make tin compound general characteristic like this in the application of being advised.By heating, perhaps be easy to realize the not dissolving on the nucleation surface of tin-oxide by the isolating thin slice of drying or by slurry being heated to higher temperature.
The successful deposition on the nucleation surface of moisture titanium dioxide or moisture zirconium dioxide requires SC, because the formation of the colloidal suspension of above-claimed cpd is easy to obtain unlike tin compound.But the technology for preparing the colloidal suspension of above-mentioned moisture metal oxide is known.For example, if with sedimentary moisture titanium dioxide washing to there not being dissolved salt, and with the final neutralization of the acid of any remnants, then resulting paste is easy to peptization and becomes colloidal suspension by adding small amount of hydrochloric acid.Similar techniques can be used for preparing the colloidal suspension of moisture zirconium dioxide, except preferred acetic acid as peptization acid.Glass flake is exposed to described colloid, and the thermal treatment that is used for not dissolving change subsequently produces effective nucleation surface.Can also in the presence of glass flake, form colloidal suspension, by with thin slice at very rare titanyl sulfate solution (based on TiO
2Content is in the order of magnitude of 0.1% concentration) middle furnishing slurry, slowly be heated to subsequently near boiling, the almost instantaneous deposition in nucleation surface.The similar fashion deposition also can be adopted in the nucleation surface of oxidizing aqueous zirconium.When using fibrous boehmite as the nucleation surface, at first must it be dispersed in the water with colloidal form by violent stirring, afterwards with glass flake furnishing slurry in described colloidal suspension, it is separated from water and be 80 ℃ or above drying in temperature.The aluminum oxide of this form, be commonly referred to fibrous boehmite, compare with the hydrated alumina that does not get transformed into fibrous boehmite and be not easy insoluble common form in diluted acid, the aspect of performance of colloidal suspension of positively charged that can be converted into sour insoluble form in its formation is very unique.
The amount of the titanium salt used with respect to treated glass flake can change in wide region and be important as the control to final oxide coating thickness only.Usually, as TiO
2The consumption that calculates can be for paramount to about 40 parts/100 parts glass flakes, for TiO from about 4 parts/100 parts glass flakes
2Preferable range be about 4-20 part/100 parts of glass flakes.Certainly, TiO
2Consumption be reflected in the thickness and the resulting interference color aspect of sedimentary layer.Following table 2 has been listed for TiO
2The analysis of a series of samples, fairly obvious, the TiO of actual deposition on glass flake
2Amount and resulting interference color between have mutual relationship.
Table 2
| Color | TiO 2Per-cent |
| The silver color thin slice | 3.0 |
| Golden thin slice | 5.8 |
| The purple thin slice | 7.4 |
| Blue thin slice | 8.6 |
The semitransparent layer of having found the outside can change in about 20 nanometers-Yue 250 nanometer range aspect the thickness so that the production color increases the product that changes with bed thickness.
On effect pigment of the present invention, can need external treatment.The example of useful external treatment is disclosed in the US patent 5,156,889,5,423,912 and 5,759,255 that is transferred to same transferee, at this it is introduced in full with for referencial use.
Product of the present invention all has purposes in all types of car paint application facet.For example, these effect pigments can mass-tones or are used to spray all types of automobiles and non-automobile as decorations (styling agent).Similarly, they can use on all clay/formica/wood/glass/metals/enamel/pottery and atresia or porous surface.This effect pigment can be used for coating composition or mixes in the plastics of toy industry usefulness or family expenses.Described effect pigment can be impregnated in the fiber to give clothing and carpet new painted with U.S..They can be used for improving the outward appearance of footwear, rubber and plastics/marble floor, plastics wallboard and all other plastic prods.In addition, these colors can be used for all types of model hobbies.Because temperature, pH, shearing, cost and can not obtain high total solid content under the situation of not destroying crystalline texture, natural pearlescent pigments only has limited industrial application again.
The above-mentioned composition that composition of the present invention can be used for wherein is known to a person of ordinary skill in the art.Example comprises printing-ink, nail varnish, lacquer, thermoplasticity and thermosetting material, natural resin and synthetic resins.Some non-limiting examples comprise polystyrene and mixed polymer thereof, polyolefine, particularly polyethylene and polypropylene, polyacrylic compounds, polyvinyl compound, for example polyvinyl chloride and polyvinyl acetate (PVA), polyester and rubber, also have fibril, cellulose ester, polymeric amide, urethane, polyester, for example polyethylene terephthalate and polyacrylonitrile by viscose glue and ether of cellulose preparation.
In order to introduce various pigment applications all-sidely, edit ThePigment Handbook, vol.II, Applications and Markets, John Wiley andSons, New York (1973) referring to Temple C.Patton.In addition, about printing ink for example referring to: R.H.Leach edits, ThePrinting Ink Manual, Fourth Edition, Van Nostrand Reinhold (International) Co.Ltd., London (1988), particularly 282-591 page or leaf; About coating: C.H.Hare, Protective Coatings, Technology Publishing Co., Pittsbrugh (1994), particularly 63-288 page or leaf.Above-mentioned reference is introduced with for referencial use,, comprised the amount of tinting material because they have instructed printing ink, coating and plastics composite, preparation and the automobile that wherein can use composition of the present invention.
At cosmetic field, this effect material can be used in all makeup and personal care application, certainly, should satisfy all laws and regulations requirements.Therefore, they can be used on hair spray, shank makeup, expelling parasite water, eyelashes cake/cream, nail varnish, enamel remover, perfume and all types of shampoo (gel or liquid).In addition, they can be used for shaving cream (brushless, foam, aerocolloidal enriched material), skin Lightening cream (skin glosser stick), skin cosmetic, hair and modify emulsion and ultra light sun block lotion after makeup, eye shadow (liquid, face cream (pomade), cream, cake (pressed) or breast), eye liner pencil, ancient imperial balm, Gu Longshui, ancient imperial softener, foam bath agent, toner (preserve moisture, cleaning, pain relieving, convergence), latex emulsion after shaving, the bath.
For the comment of cosmetic applications, referring to Cosmetics:Science and Technology, 22
NdEd., Eds:M.S.Balsam and Edward Sagarin, Wiley-Interscience (1972) and deNavarre, The Chemistry and Science of Cosmetics, 2
NdEd., Vols.1 and 2 (1962), Van Nostrand Co Inc., and Vols.3 and 4 (1975), Continental Press, both introduce with for referencial use with it at this.
The present invention various indefiniteness embodiment have been listed below in order further to explain.In these embodiment and this specification sheets and claims, all umbers and percentage number average by weight and all temperature all in degree centigrade, unless otherwise indicated.
Claims (10)
1. effect pigment that comprises the synthetic thin layer platelet that is coated with the semi-transparent metals oxide film, the distribution of sizes of described synthetic thin layer platelet is characterized by D10 and is at least 9.5 microns, D50 about 20 and less than 40 microns between, D90 is for surpassing 50 to less than 85 microns.
2. the effect pigment of claim 1, wherein said distribution of sizes is essentially Gaussian distribution.
3. the effect pigment of claim 1, wherein said synthetic thin layer platelet matrix comprises glass flake.
4. the effect pigment of claim 1, wherein said metal oxide film comprises titanium dioxide.
5. the effect pigment of claim 1, wherein said metal oxide film comprises ferric oxide.
6. the effect pigment of claim 1, its D10 is about 9.5 microns, and D50 is about 22 microns, and D90 is about 45 microns.
7. the effect pigment of claim 1, wherein said synthetic thin layer platelet is selected from aluminum oxide, silicon-dioxide, pearl white, boron nitride and glass.
8. the effect pigment of claim 1, wherein said metal oxide is titanium dioxide, ferric oxide, zirconium white, chromic oxide, nickel oxide, cobalt oxide, stannic oxide or its combination.
9. adopt the painted makeup of effect pigment of claim 1.
10. adopt the painted coating that is applicable to automobile of effect pigment of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66727605P | 2005-04-01 | 2005-04-01 | |
| US60/667,276 | 2005-04-01 | ||
| US11/277,897 | 2006-03-29 |
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|---|---|
| CN101189306A true CN101189306A (en) | 2008-05-28 |
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|---|---|---|---|
| CNA2006800195427A Pending CN101189306A (en) | 2005-04-01 | 2006-03-31 | Sparkle effect of unique particle size distribution |
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