US20210163753A1 - Composite pigments - Google Patents
Composite pigments Download PDFInfo
- Publication number
- US20210163753A1 US20210163753A1 US17/139,532 US202017139532A US2021163753A1 US 20210163753 A1 US20210163753 A1 US 20210163753A1 US 202017139532 A US202017139532 A US 202017139532A US 2021163753 A1 US2021163753 A1 US 2021163753A1
- Authority
- US
- United States
- Prior art keywords
- oxide
- component
- composite pigment
- metal oxide
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 117
- 239000000049 pigment Substances 0.000 title claims abstract description 88
- 239000003973 paint Substances 0.000 claims abstract description 135
- 239000000203 mixture Substances 0.000 claims abstract description 124
- 238000009472 formulation Methods 0.000 claims abstract description 109
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 68
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 115
- 239000011787 zinc oxide Substances 0.000 claims description 58
- 239000002245 particle Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011541 reaction mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 7
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002073 nanorod Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 3
- 150000001462 antimony Chemical class 0.000 claims 2
- 159000000009 barium salts Chemical class 0.000 claims 2
- 159000000003 magnesium salts Chemical class 0.000 claims 2
- 239000012702 metal oxide precursor Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 150000003754 zirconium Chemical class 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052914 metal silicate Inorganic materials 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 65
- 239000004408 titanium dioxide Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- -1 lesser than 40 nm Chemical compound 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000001912 oat gum Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- 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
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
-
- 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
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
-
- 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
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
-
- 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
- C09C1/30—Silicic acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
Definitions
- the present invention generally relates to composite pigments.
- the composite pigments may be used in a paint formulation so as to increase the opacity of the paint formulation.
- nanomaterials have been used in coating applications.
- Metal oxides like nano-titanium dioxide and silicon dioxide have been extensively used to formulate polymeric coatings to provide properties like photo-catalysis and excellent abrasion resistance.
- Titanium dioxide (TiO 2 ) is the pervasive and unchallenged pigment in the coating industry mainly due to its excellent ability to scatter visible light.
- TiO 2 has very high refractive index and has been commonly used to enhance the opacity of paints.
- the price of TiO 2 in recent years has fluctuated very widely and increased substantially. This prevents TiO 2 -based paints from being economically competitive.
- conventional paints for external architectural use often experience “yellowing” due to the exposure to solar radiation. High humidity and frequent rainfall in the tropical region also result in bacterial and algae growth on walls.
- the opacity or hiding power of paints depends on numerous factors such as particle size, crystalline phase of pigment, refractive index of pigments and polymer, and the dispersion or crowding of individual pigment particles. All these factors influence the back scattering of the light by individual pigment particles. Pigment crowding of TiO 2 is the most important consideration in designing of paints. This is because even though TiO 2 confers opacity to the paints, by increasing the TiO 2 content in the paint above a certain point, the pigment particles are brought to close proximity of each other, thereby interfering with the ability of such pigments to scatter light efficiently.
- extender pigments possessing smaller dimensions are used as spacer units to isolate TiO 2 pigments and increase the hiding power of the paints.
- the concept of using the spacer material along with TiO 2 pigments to improve opacity of the paint has been known for some time.
- Other known products physically coat the TiO 2 pigment to enhance the separation.
- Clays may also be used for such an application as they have high surface area.
- clays as spacer material also tend to decrease the gloss of the final paint film and alter rheological properties of the paint.
- commercial micron sized zinc oxide particles with a refractive index of 2.01 can be used as the pigment.
- commercial micron-sized zinc oxide possesses larger average particle dimensions and thus, suffers from lower surface area.
- commercial micron-sized zinc oxide has little or negligible power to influence the opacity provided by TiO 2 pigments.
- nano-sized zinc oxide particles are able to increase the opacity of a paint formulation, such paint formulations have been shown to be unstable (as evidenced by the increase in the viscosity of the paint formulation to the point of gelation) when stored for long periods of time such as two to three months.
- formulation of water based paints using ZnO requires careful consideration of various parameters and materials.
- pigments such as white lead, zinc sulphide, lithopone and antimony oxide have also been used as alternative pigments in paints.
- TiO 2 pigments are always ultimately chosen due to its higher refractive index.
- a paint formulation comprising a composite pigment, said composite pigment being selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia, wherein the size and amount of said composite pigment are selected to increase the opacity of said paint formulation.
- the composite pigment may have opaque properties and hence may be used to maintain or enhance the opacity of the paint or paint formulation.
- the composite pigment may reduce the amount of titanium dioxide that is required in the paint formulation due to the opaque properties of the composite pigment.
- the composite pigment may be an alternative to titanium dioxide. Due to the replacement of the more expensive titanium dioxide with the composite, the costs of producing the paint or paint formulation may be effectively reduced.
- the composite pigment may not affect the stability of the paint formulation.
- the composite pigment may at least maintain the stability of the paint formulation or may increase the stability of the paint formulation.
- the composite pigment may be able to enhance the opacity of the paint formulation while not affecting the stability of the paint formulation, or have any detrimental effect on the stability of the paint formulation. This is compared to prior art opacity enhancing agents in which the stability of the paint formulation decreases over time.
- the composite pigment may be able to maintain or enhance the stability of the paint or paint formulation when stored for a period of time.
- the composite may enable the paint or paint formulation to be resistant to viscosity changes.
- the composite may prevent or at least reduce the gelation or agglomeration of the paint or paint formulation during storage for a period of time.
- a method for preparing a paint formulation comprising the step of incorporating in the paint formulation an effective amount of a composite pigment selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia in order to increase the opacity of said formulation.
- a composite pigment comprising a metal oxide as a first component and a second component selected from the group consisting of silica, silicate, alumina, metal oxide and zirconia.
- nano-sized is to be interpreted broadly to relate to an average particle size of a particle of less than about 1000 nm, less than about 300 nm, between about 200 nm to about 300 nm, between about 5 nm to about 200 nm or less, than about 100 nm.
- the particle size may refer to the diameter of the particles where they are substantially spherical.
- the particles may be non-spherical and the particle size range may refer to the equivalent diameter of the particles relative to spherical particles.
- opacity and grammatical variants thereof, is used to denote the impermeability of a coating to light.
- stable when referring to a paint or paint formulation, refers to the ability of the paint or paint formulation to be stirred to form a homogeneous liquid even when stored at long periods of time.
- the viscosity of the paint or paint formulation may be a measure of the stability of the paint or paint formulation such that a stable paint or paint formulation is considered as one in which the viscosity remains substantially constant or does not increase substantially during storage of the paint or paint formulation.
- a stable paint is one which has a viscosity increase of about less than 20 KU units.
- any paint or paint formulation that results in gelation or agglomeration when stored for a period of time is considered as “unstable
- the term “about”, in the context of concentrations of components of the formulations, typically means+/ ⁇ 5% of the stated value, more typically +/ ⁇ 4% of the stated value, more typically +/ ⁇ 3% of the stated value, more typically, +/ ⁇ 2% of the stated value, even more typically +/ ⁇ 1% of the stated value, and even more typically +/ ⁇ 0.5% of the stated value.
- range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
- the paint formulation comprises a composite pigment, said composite pigment being selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia, wherein the size and amount of said composite pigment are selected to increase the opacity of said paint formulation.
- a composite pigment comprising a metal oxide as a first component and a second component selected from the group consisting of silica, silicate, alumina, metal oxide and zirconia.
- the metal oxide in said composite may be selected from the group consisting of zinc oxide, aluminium oxide, antimony oxide, magnesium oxide, barium oxide and zirconium oxide.
- the metal oxide is zinc oxide.
- the wt % of the composite pigment in the paint formulation may be in the range of about 1 wt % to about 5 wt %, based on the total weight of the paint formulation.
- the wt % of the composite pigment in the composition may be in the range selected from the group consisting of about 1 wt % to about 4 wt %, about 1 wt % to about 3 wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt % and about 2 wt % to about 3 wt %.
- the wt % of the composite pigment may be about 2 wt %.
- the particle size of the metal oxide in the composite pigment may be in the nano-range.
- the particle size of the metal oxide in the composite may be in the range selected from the group consisting of about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 60 nm, about 5 nm to about 40 nm, about 5 nm to about 20 nm, about 20 nm to about 100 nm, about 40 nm to about 100 nm, about 60 nm to about 100 nm and about 80 nm to about 100 nm.
- the particle size of the metal oxide in the composite may be about 10 nm.
- the surface area of the composite may be selected from the range of about 20 m 2 /g to about 100 m 2 /g, about 20 m 2 /g to about 80 m 2 /g, about 20 m 2 /g to about 60 m 2 /g, about 20 m 2 /g to about 40 m 2 /g, about 40 m 2 /g to about 100 m 2 /g, about 60 m 2 /g to about 100 m 2 /g or about 80 m 2 /g to about 100 m 2 /g.
- the composite may be made either in a two-step method or in a one-step method.
- the metal oxide particles are formed first followed by precipitation or coating with the silica or alumina on the metal oxide.
- the zinc oxide may be made by mixing zinc salts in a base and collecting the precipitates of zinc oxide formed.
- a surfactant or dispersant may be added to reduce the particle size of the zinc oxide particles such that the formed zinc oxide particles are in the nano-range.
- the zinc salt used may be selected from the group consisting of zinc nitrate salt (such as zinc nitrate hexahydrate), zinc acetate and zinc chloride.
- the base may be selected from the group consisting of sodium hydroxide, potassium hydroxide or calcium hydroxide.
- the method to make the zinc oxide is not limited to the above method and can encompass any method known to form nano-sized zinc oxide particles.
- an amine surfactant may be added to create a charge on the zinc oxide particles.
- Silica or alumina (or their precursors) is then added to form a composite with the zinc oxide.
- a charge modifier may be added.
- the charge modifier may be aluminium chloride solution which functions to precipitate or coat silica on the zinc oxide particles by disturbing its residual charge.
- the one step method may involve a reaction mixture comprising a metal salt, a base solution and a precursor of silica or alumina.
- the metal salt may be zinc salt selected from the group consisting of zinc nitrate salt (such as zinc nitrate hexahydrate), zinc acetate and zinc chloride.
- a surfactant or dispersant may be added to reduce the particle size of the zinc oxide particles such that the formed zinc oxide particles are in the nano-range.
- the base may be selected from the group consisting of sodium hydroxide, potassium hydroxide or calcium hydroxide.
- the pH of the reaction mixture may be adjusted appropriately.
- the pH of the reaction may be in the range of 7 to 10.
- the silica precursor may be sodium silicate solution while the alumina precursor may be aluminium chloride hexa hydrate, Sodium aluminate or colloidal alumina.
- the composite may be separated from the reaction mixture by filtration or centrifugation.
- the composite may be washed with water and dried.
- the silica, silicate, zirconia or alumina may be formed as a coating that at least partially surrounds the metal oxide particle.
- the metal oxide component may be at least partially covered by the silica, silicate, zirconia or alumina (that is, the second component)
- the metal oxide particle may be dispersed or embedded in the silica, silicate, zirconia or alumina phase.
- the silica, silicate, zirconia or alumina phase may be a continuous phase.
- the silica phase may be a continuous amorphous phase.
- the composite may have a homogeneous morphology or an inhomogeneous morphology.
- the composite may have a multifaceted homogeneous morphology.
- the composite may be a mixture of nanorods and multifaceted (inhomogeneous) morphology.
- the zinc oxide in the composite is zinc oxide
- the zinc oxide may have a hexagonal structure
- the composite pigment may be of the core-shell structure.
- the core of the core-shell structure may be hollow or empty while the shells of the core-shell structure are made up of alternating layers of the metal oxide layer (or first component layer) and silica, silicate, zirconia, metal oxide or alumina layer (or second component layer).
- the silica, silicate, zirconia, metal oxide or alumina layer (or second component layer) may at least partially cover the metal oxide layer (or first component layer).
- the number of layers is not particularly limited.
- the difference in refractive indices of different layered materials improves the back scattering of light.
- more substantial difference in refractive index are created by forming a hollow layered inorganic composite pigment. Such a pigment upon drying leaves a hollow space that helps in better back scattering of light, leading to better opacity.
- the composite may act as a substitute for titanium dioxide in the paint formulation while keeping the opacity of the paint formulation substantially the same or even increased as compared to a conventional paint formulation without the composite.
- the composite may maintain or enhance the stability of the paint formulation while maintaining or increasing the opacity of the paint formulation.
- the composite may act as a substitute to replace up to 30% of titanium dioxide particles in the paint formulation.
- the composite may replace up to 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% of the titanium dioxide particles in the paint formulation.
- the paint formulation may have an opacity in the range selected from the group consisting of greater than 85%, greater than 86%, greater than 87%, greater than 88%, greater than 89%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98% and greater than 99%.
- the substitution of conventional titanium dioxide particles with the composite may not substantially affect the opacity of the paint formulation. Accordingly, it is possible to use a lesser amount of the titanium dioxide, which is typically used to make paint coatings opaque, without compromising on the opacity and/or stability of the paint formulation.
- the paint formulation may have substantially the same opacity or increased opacity as compared to another paint formulation without the composite.
- the metal oxide in said composite may be selected from the group consisting of zinc oxide, barium oxide, aluminium oxide, antimony oxide, magnesium oxide and zirconium oxide. In one embodiment, the metal oxide is zinc oxide.
- the composite pigment may be toxic to microbes and hence may have an anti-microbial (such as anti-bacterial or anti-fungal) effect.
- the composite pigment in a paint formulation may be able to enhance the opacity of the paint formulation while maintaining or enhancing the stability of the paint formulation.
- the composite pigment may be able to exert an anti-microbial effect so as to increase the durability and life-time of the paint formulation.
- the anti-microbial effect of the composite pigment may also be expanded to the dried paint.
- the composite having a metal oxide such as zinc oxide may function as a UV absorbent and may confer anti-microbial properties to the paint formulation. This may be due to the particle size of the zinc oxide, such as lesser than 40 nm, which result in these properties. Hence, the overall durability of the paint formulation may be improved with the incorporation of the composite in the paint formulation.
- the paint formulation may be an acrylic water based paint, a water based vinyl paint, a polyurethane paint, an alkyd paint, a thermosetting paint and a solvent based paint.
- a method for preparing a paint formulation comprising the step of incorporating in the paint formulation an effective amount of a composite pigment selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia in order to increase the opacity of said formulation.
- the effective amount of the composite pigment in the paint formulation may be in the range of 1 wt % to 5 wt %, based on the total weight of the paint formulation.
- FIG. 1 shows the X-Ray Diffraction (XRD) pattern of silica coated on nano zinc oxide composite formed in accordance with Example 2.
- FIG. 2 shows a transmission electron micrograph (TEM) of silica coated on nano zinc oxide composite formed in accordance with Example 2.
- FIG. 2( a ) is at low magnification
- FIG. 2( b ) is at a higher magnification
- FIG. 2( c ) is at high resolution.
- the magnifications of these figures are indicated indirectly by the “line scale” corresponding to the size in nano-meter.
- FIG. 3 shows a XRD pattern of alumina coated on nano zinc oxide composite formed in accordance with Example 4.
- FIG. 4 shows a TEM of alumina coated on nano zinc oxide composite formed in accordance with Example 4.
- FIG. 4( a ) is at low magnification
- FIG. 4( b ) is at higher magnification
- FIG. 4( c ) is at high resolution.
- the magnifications of these figures are indicated indirectly by the “line scale” corresponding to the size in nano-meter.
- FIG. 5 is a X-ray diffraction pattern of the nano zinc oxide obtained in Comparative Example 1.
- FIGS. 6 and 7 are scanning electron microscopy images showing the hollow silica-based composite particles.
- the dried solid was powdered and characterised using BET surface area analysis (21.97 m 2 /g), XRD (see FIG. 1 ) and TEM ( FIG. 2 ).
- the nano-ZnO-silica composite obtained from Example 1 together with titanium dioxide (TiO 2 ) as the main pigment was used to formulate an acrylic water-based paint.
- the formulation was named “N—ZnO-silica composite Formulation”.
- the weight of the TiO 2 present in this formulation was reduced as compared to that present in the Standard Formulation described below.
- a comparative acrylic water-based paint formulation based on TiO 2 pigments alone was made. This formulation was named “Standard Formulation”.
- Contrast Ratio was measured using the ZEHNTNER Reflectometer (Zehntner Testing Instruments, Switzerland). Accelerated storage studies were made by storing the paint at 60° C. for fourteen days and assessing the paint appearance visually for any cake formation, hard settlement and paint flow.
- the stability and opacity of the paint formulation with the composite are comparable to that of the paint formulation without the composite.
- the composite can reduce the amount of titanium dioxide required by about 27%, leading to cost savings.
- the surface area of the powder from the dried solid was 78.9 m 2 /g.
- the XRD pattern and TEM of nano-ZnO-alumina composited are shown in FIG. 3 and FIG. 4 respectively.
- the TEM images ( FIG. 4( a ) , FIG. 4( b ) ) showed that the synthesized powder was multifaceted phase.
- the inter-planar spacing (see FIG. 4( c ) ) was 2.5 ⁇ and was close to the inter-planar spacing of (002) plane of ZnO (2.6 ⁇ ).
- Nano Calcium Carbonate obtained from Nano Materials Technology Pte Ltd, Singapore
- Tetra ethyl ortho silicate obtained from Sinopharm Chemical Reagent Company Limited, China
- pH was adjusted to 8.5 with ammonia.
- the reaction mixture was then stirred for 1 hour and pH was adjusted to 6 by slowly adding glacial acetic acid. After all the carbon dioxide evolution ceases, the sample of hollow silica was isolated by filtration and drying.
- the above reaction can directly be converted into hollow silica-zinc oxide-silica composite pigment.
- About 408 grams of anhydrous zinc chloride was dissolved in the reaction mixture followed by Indoemul co-02 (0.25 grams).
- 450 grams of 54% sodium hydroxide solution was added for 2.5 hours.
- the reaction mixture was stirred for additional 2 hours and pH was adjusted to 8-8.5
- About 33 grams of colloidal silica was added to this reaction mixture and stirred for 1 hour.
- hollow composite pigment was filtered and washed with water and dried in oven at 80 degree Celsius.
- the reaction mixture was then filtered and washed with water till the filtrate showed a pH of 7.
- the solid residue material obtained was dried in an oven at 80° C. and grounded to get fine white powder.
- the fine white powder was analyzed by X-ray diffraction (XRD) and the XRD pattern is shown in FIG. 5 .
- XRD X-ray diffraction
- the XRD pattern confirms that pure zinc oxide (ZnO) was obtained.
- ZnO pure zinc oxide
- the three main 2 Theta peak values in FIG. 5 are at 31.72; 34.45; and 36.21, which correspond to standard ZnO peaks as mentioned in the Joint Committee on Powder Diffraction Standards (JCPDS) Card No. 36-1451 P6 3 mc space group.
- the fine white powder was also analyzed by the Brunauer-Emmett-Teller (BET) method.
- BET Brunauer-Emmett-Teller
- n-ZnO nano zinc oxide
- TiO 2 titanium dioxide
- Standard Formulation The nano zinc oxide (n-ZnO) together with titanium dioxide (TiO 2 ) as the main pigment was used to formulate an acrylic water-based paint.
- the formulation was named “n-ZnO Formulation”.
- the weight of the TiO 2 present in this formulation was 70% of that present in the Standard Formulation described below.
- a comparative acrylic water-based paint formulation based on TiO 2 pigments alone was made. This formulation was named “Standard Formulation”.
- Contrast Ratio was measured using the ZEHNTNER Reflectometer, (Zehntner Testing Instruments, Switzerland). Accelerated storage studies were made by storing the paint at 60° C. for fourteen days and assessing the paint appearance visually for any cake formation, hard settlement and paint flow.
- the disclosed composition advantageously enhances the stability of a paint formulation without depriving the paint formulations from being economically feasible to produce or affecting the opacity of the paint formulation.
- the disclosed composition permits a lower amount of expensive raw material required in paint formulations without depriving the paint formulations of the properties required.
- the composite of the present disclosure can be used as a partial replacement for the relatively more expensive titanium dioxide pigment in paint formulations.
- the disclosed composition possesses improved durability against the natural elements.
- the disclosed composite confers anti-bacterial properties to the composition.
- the disclosed composite improves the ultraviolet resistance of the composition, thereby conferring durability to the composition.
- the disclosed composite does not leach out of the composition.
- the disclosed composite of the present disclosure can be used as partial replacement for conventional ZnO in the vulcanization of rubber.
- the disclosed composite of the present disclosure can be used as a wide band width semiconductor in certain electronic applications.
- the disclosed composite of the present disclosure can also be used to improve abrasion and wear resistance in polymer composites whether alone or in combination with other nanomaterials such as clay.
- the disclosed composite of the present disclosure can be dispersed in organic solvents and polymers to improve the durability of organic polymer composites to the natural elements.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Silicon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
- The present invention generally relates to composite pigments. The composite pigments may be used in a paint formulation so as to increase the opacity of the paint formulation.
- The application of nanomaterials to various industrial uses has gathered substantial interest both industrially and academically. The main motivating force for this momentum is the ability of nanomaterials, with their near-atomic dimensions, to substantially improve the properties of final products.
- For example, nanomaterials have been used in coating applications. Metal oxides like nano-titanium dioxide and silicon dioxide have been extensively used to formulate polymeric coatings to provide properties like photo-catalysis and excellent abrasion resistance.
- Titanium dioxide (TiO2) is the pervasive and unchallenged pigment in the coating industry mainly due to its excellent ability to scatter visible light. Thus, TiO2 has very high refractive index and has been commonly used to enhance the opacity of paints. However, the price of TiO2 in recent years has fluctuated very widely and increased substantially. This prevents TiO2-based paints from being economically competitive. Furthermore, conventional paints for external architectural use often experience “yellowing” due to the exposure to solar radiation. High humidity and frequent rainfall in the tropical region also result in bacterial and algae growth on walls.
- The opacity or hiding power of paints depends on numerous factors such as particle size, crystalline phase of pigment, refractive index of pigments and polymer, and the dispersion or crowding of individual pigment particles. All these factors influence the back scattering of the light by individual pigment particles. Pigment crowding of TiO2 is the most important consideration in designing of paints. This is because even though TiO2 confers opacity to the paints, by increasing the TiO2 content in the paint above a certain point, the pigment particles are brought to close proximity of each other, thereby interfering with the ability of such pigments to scatter light efficiently.
- To overcome the problem of pigment crowding, extender pigments possessing smaller dimensions are used as spacer units to isolate TiO2 pigments and increase the hiding power of the paints.
- The concept of using the spacer material along with TiO2 pigments to improve opacity of the paint has been known for some time. For example, there is a known product that uses differences in refractive index between the different materials to increase scattering. Other known products physically coat the TiO2 pigment to enhance the separation. Clays may also be used for such an application as they have high surface area. However, it has been difficult to practice such applications commercially due to requirement of large amount of spacer material leading to high comparative cost of the paint. Furthermore clays as spacer material also tend to decrease the gloss of the final paint film and alter rheological properties of the paint.
- Alternatively commercial micron sized zinc oxide particles with a refractive index of 2.01 can be used as the pigment. However, commercial micron-sized zinc oxide possesses larger average particle dimensions and thus, suffers from lower surface area. As a result, commercial micron-sized zinc oxide has little or negligible power to influence the opacity provided by TiO2 pigments. In addition, while nano-sized zinc oxide particles are able to increase the opacity of a paint formulation, such paint formulations have been shown to be unstable (as evidenced by the increase in the viscosity of the paint formulation to the point of gelation) when stored for long periods of time such as two to three months. In addition, formulation of water based paints using ZnO requires careful consideration of various parameters and materials. The interaction of ZnO with TiO2 is very strong under the alkaline pH range that normally prevails in water based paints. This invariably results in poor stability of the paint leading to progressive increase in viscosity and possible irreversible gelling at room temperature. The paint often fails in accelerated storage test conducted at 60° C. for 14 days.
- Further, other pigments such as white lead, zinc sulphide, lithopone and antimony oxide have also been used as alternative pigments in paints. However, TiO2 pigments are always ultimately chosen due to its higher refractive index.
- There is, therefore, a need to provide paint formulations that overcomes, or at least ameliorates, one or more of the disadvantages described above. There is a need to provide stable paint formulations that overcomes, or at least ameliorates, one or more of the disadvantages described above.
- According to a first aspect, there is provided a paint formulation comprising a composite pigment, said composite pigment being selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia, wherein the size and amount of said composite pigment are selected to increase the opacity of said paint formulation.
- The composite pigment may have opaque properties and hence may be used to maintain or enhance the opacity of the paint or paint formulation. The composite pigment may reduce the amount of titanium dioxide that is required in the paint formulation due to the opaque properties of the composite pigment. Hence, the composite pigment may be an alternative to titanium dioxide. Due to the replacement of the more expensive titanium dioxide with the composite, the costs of producing the paint or paint formulation may be effectively reduced.
- As the composite pigment enhances the opacity of the paint formulation, the composite pigment may not affect the stability of the paint formulation. Hence, the composite pigment may at least maintain the stability of the paint formulation or may increase the stability of the paint formulation. Hence, the composite pigment may be able to enhance the opacity of the paint formulation while not affecting the stability of the paint formulation, or have any detrimental effect on the stability of the paint formulation. This is compared to prior art opacity enhancing agents in which the stability of the paint formulation decreases over time.
- The composite pigment may be able to maintain or enhance the stability of the paint or paint formulation when stored for a period of time. The composite may enable the paint or paint formulation to be resistant to viscosity changes. The composite may prevent or at least reduce the gelation or agglomeration of the paint or paint formulation during storage for a period of time.
- In a second aspect, there is provided a method for preparing a paint formulation comprising the step of incorporating in the paint formulation an effective amount of a composite pigment selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia in order to increase the opacity of said formulation.
- In a third aspect, there is provided a composite pigment comprising a metal oxide as a first component and a second component selected from the group consisting of silica, silicate, alumina, metal oxide and zirconia.
- The following words and terms used herein shall have the meaning indicated:
- The term “nano-sized” is to be interpreted broadly to relate to an average particle size of a particle of less than about 1000 nm, less than about 300 nm, between about 200 nm to about 300 nm, between about 5 nm to about 200 nm or less, than about 100 nm. The particle size may refer to the diameter of the particles where they are substantially spherical. The particles may be non-spherical and the particle size range may refer to the equivalent diameter of the particles relative to spherical particles.
- The term “opacity”, and grammatical variants thereof, is used to denote the impermeability of a coating to light.
- The term “stable”, when referring to a paint or paint formulation, refers to the ability of the paint or paint formulation to be stirred to form a homogeneous liquid even when stored at long periods of time. The viscosity of the paint or paint formulation may be a measure of the stability of the paint or paint formulation such that a stable paint or paint formulation is considered as one in which the viscosity remains substantially constant or does not increase substantially during storage of the paint or paint formulation. During accelerated storage experiments, a stable paint is one which has a viscosity increase of about less than 20 KU units. For the avoidance of doubt, any paint or paint formulation that results in gelation or agglomeration when stored for a period of time is considered as “unstable
- The word “substantially” does not exclude “completely” e.g. a composition which is “substantially free” from Y may be completely free from Y. Where necessary, the word “substantially” may be omitted from the definition of the invention.
- Unless specified otherwise, the terms “comprising” and “comprise”, and grammatical, variants thereof, are intended to represent “open” or “inclusive” language such that they include recited elements but also permit inclusion of additional, unrecited elements.
- As used herein, the term “about”, in the context of concentrations of components of the formulations, typically means+/−5% of the stated value, more typically +/−4% of the stated value, more typically +/−3% of the stated value, more typically, +/−2% of the stated value, even more typically +/−1% of the stated value, and even more typically +/−0.5% of the stated value.
- Throughout this disclosure, certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
- Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
- Exemplary, non-limiting embodiments of a paint formulation will now be disclosed. The paint formulation comprises a composite pigment, said composite pigment being selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia, wherein the size and amount of said composite pigment are selected to increase the opacity of said paint formulation.
- There is also provided a composite pigment comprising a metal oxide as a first component and a second component selected from the group consisting of silica, silicate, alumina, metal oxide and zirconia. The metal oxide in said composite may be selected from the group consisting of zinc oxide, aluminium oxide, antimony oxide, magnesium oxide, barium oxide and zirconium oxide. In one embodiment, the metal oxide is zinc oxide.
- The wt % of the composite pigment in the paint formulation may be in the range of about 1 wt % to about 5 wt %, based on the total weight of the paint formulation. The wt % of the composite pigment in the composition may be in the range selected from the group consisting of about 1 wt % to about 4 wt %, about 1 wt % to about 3 wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt % and about 2 wt % to about 3 wt %. In one embodiment, the wt % of the composite pigment may be about 2 wt %.
- The particle size of the metal oxide in the composite pigment may be in the nano-range. The particle size of the metal oxide in the composite may be in the range selected from the group consisting of about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 5 nm to about 60 nm, about 5 nm to about 40 nm, about 5 nm to about 20 nm, about 20 nm to about 100 nm, about 40 nm to about 100 nm, about 60 nm to about 100 nm and about 80 nm to about 100 nm. In one embodiment, the particle size of the metal oxide in the composite may be about 10 nm.
- The surface area of the composite may be selected from the range of about 20 m2/g to about 100 m2/g, about 20 m2/g to about 80 m2/g, about 20 m2/g to about 60 m2/g, about 20 m2/g to about 40 m2/g, about 40 m2/g to about 100 m2/g, about 60 m2/g to about 100 m2/g or about 80 m2/g to about 100 m2/g.
- The composite may be made either in a two-step method or in a one-step method. In the two-step method, the metal oxide particles are formed first followed by precipitation or coating with the silica or alumina on the metal oxide. Where the metal oxide is zinc oxide, the zinc oxide may be made by mixing zinc salts in a base and collecting the precipitates of zinc oxide formed. A surfactant or dispersant may be added to reduce the particle size of the zinc oxide particles such that the formed zinc oxide particles are in the nano-range. The zinc salt used may be selected from the group consisting of zinc nitrate salt (such as zinc nitrate hexahydrate), zinc acetate and zinc chloride. The base may be selected from the group consisting of sodium hydroxide, potassium hydroxide or calcium hydroxide. It is to be appreciated that the method to make the zinc oxide is not limited to the above method and can encompass any method known to form nano-sized zinc oxide particles. Following which, an amine surfactant may be added to create a charge on the zinc oxide particles. Silica or alumina (or their precursors) is then added to form a composite with the zinc oxide. To enhance the precipitation or coating of the silica or alumina on the zinc oxide particles, a charge modifier may be added. The charge modifier may be aluminium chloride solution which functions to precipitate or coat silica on the zinc oxide particles by disturbing its residual charge.
- The one step method may involve a reaction mixture comprising a metal salt, a base solution and a precursor of silica or alumina. Where the metal oxide to be formed is zinc oxide, the metal salt may be zinc salt selected from the group consisting of zinc nitrate salt (such as zinc nitrate hexahydrate), zinc acetate and zinc chloride. A surfactant or dispersant may be added to reduce the particle size of the zinc oxide particles such that the formed zinc oxide particles are in the nano-range. The base may be selected from the group consisting of sodium hydroxide, potassium hydroxide or calcium hydroxide. During formation of the composite, the pH of the reaction mixture may be adjusted appropriately. The pH of the reaction may be in the range of 7 to 10. By adjusting the pH of the reaction during formation of the composite, uniform coating of the metal oxide particles can be achieved. The silica precursor may be sodium silicate solution while the alumina precursor may be aluminium chloride hexa hydrate, Sodium aluminate or colloidal alumina.
- Once the composite is formed, the composite may be separated from the reaction mixture by filtration or centrifugation. The composite may be washed with water and dried.
- The silica, silicate, zirconia or alumina may be formed as a coating that at least partially surrounds the metal oxide particle. Hence, the metal oxide component may be at least partially covered by the silica, silicate, zirconia or alumina (that is, the second component)
- The metal oxide particle may be dispersed or embedded in the silica, silicate, zirconia or alumina phase. The silica, silicate, zirconia or alumina phase may be a continuous phase. The silica phase may be a continuous amorphous phase.
- The composite may have a homogeneous morphology or an inhomogeneous morphology. The composite may have a multifaceted homogeneous morphology. The composite may be a mixture of nanorods and multifaceted (inhomogeneous) morphology.
- Where the metal oxide in the composite is zinc oxide, the zinc oxide may have a hexagonal structure.
- The composite pigment may be of the core-shell structure. The core of the core-shell structure may be hollow or empty while the shells of the core-shell structure are made up of alternating layers of the metal oxide layer (or first component layer) and silica, silicate, zirconia, metal oxide or alumina layer (or second component layer). The silica, silicate, zirconia, metal oxide or alumina layer (or second component layer) may at least partially cover the metal oxide layer (or first component layer). The number of layers is not particularly limited.
- In the above embodiments, the difference in refractive indices of different layered materials improves the back scattering of light. In the core-shell structure, more substantial difference in refractive index are created by forming a hollow layered inorganic composite pigment. Such a pigment upon drying leaves a hollow space that helps in better back scattering of light, leading to better opacity.
- The composite may act as a substitute for titanium dioxide in the paint formulation while keeping the opacity of the paint formulation substantially the same or even increased as compared to a conventional paint formulation without the composite. The composite may maintain or enhance the stability of the paint formulation while maintaining or increasing the opacity of the paint formulation.
- The composite may act as a substitute to replace up to 30% of titanium dioxide particles in the paint formulation. The composite may replace up to 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% of the titanium dioxide particles in the paint formulation.
- The paint formulation may have an opacity in the range selected from the group consisting of greater than 85%, greater than 86%, greater than 87%, greater than 88%, greater than 89%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98% and greater than 99%. Hence, the substitution of conventional titanium dioxide particles with the composite may not substantially affect the opacity of the paint formulation. Accordingly, it is possible to use a lesser amount of the titanium dioxide, which is typically used to make paint coatings opaque, without compromising on the opacity and/or stability of the paint formulation.
- The paint formulation may have substantially the same opacity or increased opacity as compared to another paint formulation without the composite.
- The metal oxide in said composite may be selected from the group consisting of zinc oxide, barium oxide, aluminium oxide, antimony oxide, magnesium oxide and zirconium oxide. In one embodiment, the metal oxide is zinc oxide.
- The composite pigment may be toxic to microbes and hence may have an anti-microbial (such as anti-bacterial or anti-fungal) effect. Hence, the composite pigment in a paint formulation may be able to enhance the opacity of the paint formulation while maintaining or enhancing the stability of the paint formulation. At the same time, the composite pigment may be able to exert an anti-microbial effect so as to increase the durability and life-time of the paint formulation. When the paint formulation is applied to a surface and dried, the anti-microbial effect of the composite pigment may also be expanded to the dried paint.
- The composite having a metal oxide such as zinc oxide may function as a UV absorbent and may confer anti-microbial properties to the paint formulation. This may be due to the particle size of the zinc oxide, such as lesser than 40 nm, which result in these properties. Hence, the overall durability of the paint formulation may be improved with the incorporation of the composite in the paint formulation.
- The paint formulation may be an acrylic water based paint, a water based vinyl paint, a polyurethane paint, an alkyd paint, a thermosetting paint and a solvent based paint.
- There is also provided a method for preparing a paint formulation comprising the step of incorporating in the paint formulation an effective amount of a composite pigment selected from the group consisting of metal oxide/silica, metal oxide/silicate, metal oxide/alumina, metal oxide/metal oxide and metal oxide/zirconia in order to increase the opacity of said formulation.
- The effective amount of the composite pigment in the paint formulation may be in the range of 1 wt % to 5 wt %, based on the total weight of the paint formulation.
- The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.
-
FIG. 1 shows the X-Ray Diffraction (XRD) pattern of silica coated on nano zinc oxide composite formed in accordance with Example 2. -
FIG. 2 shows a transmission electron micrograph (TEM) of silica coated on nano zinc oxide composite formed in accordance with Example 2.FIG. 2(a) is at low magnification,FIG. 2(b) is at a higher magnification, andFIG. 2(c) is at high resolution. The magnifications of these figures are indicated indirectly by the “line scale” corresponding to the size in nano-meter. -
FIG. 3 shows a XRD pattern of alumina coated on nano zinc oxide composite formed in accordance with Example 4. -
FIG. 4 shows a TEM of alumina coated on nano zinc oxide composite formed in accordance with Example 4.FIG. 4(a) is at low magnification,FIG. 4(b) is at higher magnification, andFIG. 4(c) is at high resolution. The magnifications of these figures are indicated indirectly by the “line scale” corresponding to the size in nano-meter. -
FIG. 5 is a X-ray diffraction pattern of the nano zinc oxide obtained in Comparative Example 1. -
FIGS. 6 and 7 are scanning electron microscopy images showing the hollow silica-based composite particles. - Non-limiting examples of the invention will be further described in greater detail by reference to specific Examples and a comparative example, which should not be construed as in any way limiting the scope of the invention.
- 204 grams of anhydrous zinc chloride (obtained from Mega chemicals, Singapore) was dissolved in 150 grams of water and 0.5 grams of Indoemul CO-02 was added to this solution and stirred at 1500 RPM for 5 minutes. 300 grams of 40% sodium hydroxide was added to this stirred solution for a period of 2.5 hours. The reaction mixture was then stirred for 2 additional hours. The pH of the reaction mixture was then adjusted to 7 to 7.5 using glacial acetic acid and 15.6 grams of sodium silicate solution (10% sodium oxide and 28% silicon dioxide, obtained from SD Fine chemicals Ltd, Mumbai of India) was added. The pH was adjusted from 10 to 8.5 and reaction mixture was stirred for one hour until pH gradually reaches 9.5. The pH was again adjusted to 7.5 and the reaction mixture was stirred for an additional one hour. The reaction mixture was then filtered and washed with water. The filtered solid was dried in an oven at 80° C. for 24 hours.
- The dried solid was powdered and characterised using BET surface area analysis (21.97 m2/g), XRD (see
FIG. 1 ) and TEM (FIG. 2 ). - From the XRD pattern of
FIG. 1 , the major peaks are at about 31.76, 34.39, 36.24, 47.52, 56.59, 62.81, 66.37 and 67.92 (° 2θ), which confirmed the presence of ZnO with hexagonal structure (space group-P63mc). Using Scherrer's equation, the crystalline size of 23.5 nm was calculated. The remaining peaks correspond to SiO2 and Zn(OH)2. From the pattern, it is evident that the formation of SiO2 was amorphous. After silica coating on ZnO, this shifted the ZnO peaks 0.02 Å towards the left side which confirmed the presence of SiO2. - From the TEM image of
FIG. 3(a) , it can be seen that the synthesized powder had an inhomogeneous morphology, which is a mixture of nanorods and multifaceted morphology. Higher magnification (seeFIG. 3(b) ) showed that the nanorods consisted of ˜10 nm ZnO embedded in a continuous amorphous SiO2 phase. The inter-planar spacing (seeFIG. 3(c) ) was 3.3 Å and was close to the inter-planar spacing of (100) plane of ZnO (3.25 Å). - About 90 grams of nano ZnO (obtained from Example 1) was suspended and stirred in 105 ml of water with 0.1 grams of tertiary amine surfactant-Coco bis (hydroxyl ethyl) amine (Indoemul CO-02, obtained from Indoamine Ltd, Baroda of India). 15 grams of a 30% solution of commercial Colloidal Silica (Bindzil, obtained from Akzo Nobel, Netherlands) was added to this suspension and stirred at 1500 rpm for 15 minutes. Then 0.7 grams of 10% aluminium chloride (obtained from Access Chemicals, Singapore) solution was added to the reaction moisture and stirred for 1 hour. The thick paste obtained was dried in an oven and used for characterization. The surface area of the powder was 23.43 m2/g.
- The nano-ZnO-silica composite obtained from Example 1 together with titanium dioxide (TiO2) as the main pigment was used to formulate an acrylic water-based paint. The formulation was named “N—ZnO-silica composite Formulation”. The weight of the TiO2 present in this formulation was reduced as compared to that present in the Standard Formulation described below. A comparative acrylic water-based paint formulation based on TiO2 pigments alone was made. This formulation was named “Standard Formulation”.
- When the TiO2 was replaced in the “N—ZnO-silica composite Formulation” with the composite, there was a decrease in the total pigment volume. This decrease in pigment volume was compensated by increasing the amount of silica and/or talc to keep the pigment volume concentration the same in the formulations shown in Table 1 below.
- Contrast Ratio was measured using the ZEHNTNER Reflectometer (Zehntner Testing Instruments, Switzerland). Accelerated storage studies were made by storing the paint at 60° C. for fourteen days and assessing the paint appearance visually for any cake formation, hard settlement and paint flow.
-
TABLE 1 Paint formulation using Nano-ZnO-silica composite Standard n-ZnO-Silica Formulation Formulation No. Materials (in grams) (in grams) 1. Thickener: Bermocoll 0.50 0.50 E411 (Akzo Nobel, Netherlands 2. Anti-Microbial Agent: 1.00 1.00 Zinc Omadine (Arch Chemicals, USA) 3. Dispersing agent: Orotan 1.00 1.00 1850E-Dow Chemicals, USA) 4. Defoamer: Dapro 7010 0.25 0.25 (Elementis Korea) 5. Water 18.94 20.34 6. n-ZnO-Silica composite -NA- 2.00 7. Titanium dioxide R900 23.00 16.67 (Dupont, USA) 8. Calcium Carbonate 3.64 5.62 9. Talc 1.87 2.82 10. Fumed Silica 0.30 0.30 11. Acrylic Resin emulsion 35.00 35.00 (UCAR ™ 352, obtained from The Dow Chemical Company, California, USA) 12. ROPAQUE ™ emulsion 12.00 12.00 (obtained from The Dow Chemical Company, California, USA) 13. Texanol (obtained from 0.70 0.70 Eastman Chemical Company, Tennessee, USA) 14. 2-Amino-2-methyl-1- 0.30 0.30 propanol + 5% water (AMP ™-95 obtained from The Dow Chemical Company, California, USA) 15 Mono Ethylene Glycol 1.00 1.00 (Dow Chemicals, USA) 16 Tergitol NP 9 (Dow 0.50 0.50 Chemicals, USA) Contrast Ratio (Opacity) 95.15 95.84 (%) Accelerated storage test Pass- Paint Pass-- with slightly homogeneous reduced flow Paint with slightly more viscosity and reduced flow - As shown in Table 1 above, the stability and opacity of the paint formulation with the composite are comparable to that of the paint formulation without the composite. In addition, the composite can reduce the amount of titanium dioxide required by about 27%, leading to cost savings.
- 68 grams of anhydrous zinc chloride was dissolved in 90 ml of water and 2.5 grams of anionic dispersing agent Coatex P90 (obtained from Arkema, USA) was added to this solution and stirred at 1500 RPM for 5 minutes. 100 grams of 40% sodium hydroxide was added to this stirred solution for a period of 2.5 hours. The reaction mixture was then stirred for 2 additional hours. The pH of the reaction mixture was then adjusted 8.5 using glacial acetic acid. About 12.2 grams of aluminium chloride hexa hydrate was added and pH of the reaction turns to 7. About 14 grams of 40% sodium hydroxide was added for fifteen minutes with very good agitation. The pH of the reaction was maintained at 8.0 to 8.5 for a period of 1.5 hours. The precipitated solid was then filtered, washed with water and dried 80 degree C. oven for 24 hours.
- The surface area of the powder from the dried solid was 78.9 m2/g. The XRD pattern and TEM of nano-ZnO-alumina composited are shown in
FIG. 3 andFIG. 4 respectively. - From the XRD pattern of the alumina coated on nano ZnO composite as shown in
FIG. 3 , the major peaks are at about 31.76, 34.39, 36.24, 47.52, 56.59, 62.81, 66.37 and 67.92 (° 2θ), which confirmed the presence of ZnO with hexagonal structure (space group-P63mc). Using Scherrer's equation, the crystalline size of 25.1 nm was calculated. Along with nano ZnO, the other phases of Al2O3 and AlZn7O10 were formed. Form the pattern, it is obvious that the crystalline phase of Al2O3 was coated on nano ZnO and which confirmed the presence of composite coating. - The TEM images (
FIG. 4(a) ,FIG. 4(b) ) showed that the synthesized powder was multifaceted phase. The inter-planar spacing (seeFIG. 4(c) ) was 2.5 Å and was close to the inter-planar spacing of (002) plane of ZnO (2.6 Å). - 30 grams of Nano Calcium Carbonate (obtained from Nano Materials Technology Pte Ltd, Singapore) was suspended in 300 ml of rapidly stirring water. About 34.8 grams of Tetra ethyl ortho silicate (obtained from Sinopharm Chemical Reagent Company Limited, China) was added and pH was adjusted to 8.5 with ammonia. The reaction mixture was then stirred for 1 hour and pH was adjusted to 6 by slowly adding glacial acetic acid. After all the carbon dioxide evolution ceases, the sample of hollow silica was isolated by filtration and drying.
- The above reaction can directly be converted into hollow silica-zinc oxide-silica composite pigment. About 408 grams of anhydrous zinc chloride was dissolved in the reaction mixture followed by Indoemul co-02 (0.25 grams). 450 grams of 54% sodium hydroxide solution was added for 2.5 hours. The reaction mixture was stirred for additional 2 hours and pH was adjusted to 8-8.5 About 33 grams of colloidal silica was added to this reaction mixture and stirred for 1 hour. At the end of the reaction, hollow composite pigment was filtered and washed with water and dried in oven at 80 degree Celsius.
-
TABLE 2 Paint formulation using Hollow silica-ZnO-silica composite Standard n-ZnO-Silica Formulation Formulation No. Materials (in grams) (in grams) 1. Thickener: Bermocoll 0.40 0.40 E411 (Akzo Nobel, Netherlands 2. Anti-Microbial Agent: 1.00 1.00 Zinc Omadine (Arch Chemicals , USA) 3. Dispersing agent: Orotan 1.00 1.00 1850E-Dow Chemicals, USA) 4. Defoamer: Dapro 7010 0.25 0.25 (Elementis Korea) 5. Water 22.54 22.14 6. Hollow Silica-ZnO-Silica -NA- 2.00 composite 7. Titanium dioxide R900 23.00 16.98 (Dupont, USA) 8. Calcium Carbonate 4.94 7.42 9. Talc 1.86 2.57 10. Fumed Silica 0.30 0.30 11. Acrylic Resin emulsion 34.00 34.00 (UCAR ™ 362, obtained from The Dow Chemical Company, California, USA) 12. ROPAQUE ™ emulsion 9.00 9.00 (obtained from The Dow Chemical Company, California, USA) 13. Texanol (obtained from 1.00 1.00 Eastman Chemical Company, Tennessee, USA) 14. 2-Amino-2-methyl-1- 0.30 0.30 propanol + 5% water (AMP ™-95 obtained from The Dow Chemical Company, California, USA) 15 Mono Ethylene Glycol 1.00 1.00 (Dow Chemicals, USA) 16 Tergitol NP 9 (Dow 0.50 0.50 Chemicals, USA) Contrast Ratio (Opacity) 95.84 95.89 (*) Accelerated storage test Pass- Paint Pass-- with slightly homogeneous reduced flow Paint with slightly more viscosity and reduced flow - 32 grams of zinc nitrate hexahydrate (obtained from Accesschem Pte Ltd, Singapore) was dissolved in 67.5 grams of methanol (obtained from Accesschem Pte Ltd, Singapore) and 40 grams of water.
- 8.7 grams of sodium hydroxide (obtained from Sigma Aldrich, Mo., United States of America) was dissolved in 40 grams of water separately and added to the zinc nitrate hexahydrate mixture slowly over a period of 1 hour and 15 minutes.
- After the addition, the reaction was stirred for 1.5 hours. Thereafter, about 120 ml of water was added and the mixture was stirred for additional 1.5 hours.
- The reaction mixture was then filtered and washed with water till the filtrate showed a pH of 7. The solid residue material obtained was dried in an oven at 80° C. and grounded to get fine white powder.
- The fine white powder was analyzed by X-ray diffraction (XRD) and the XRD pattern is shown in
FIG. 5 . FromFIG. 5 , the XRD pattern confirms that pure zinc oxide (ZnO) was obtained. Specifically, the three main 2 Theta peak values inFIG. 5 are at 31.72; 34.45; and 36.21, which correspond to standard ZnO peaks as mentioned in the Joint Committee on Powder Diffraction Standards (JCPDS) Card No. 36-1451 P63 mc space group. - The fine white powder was also analyzed by the Brunauer-Emmett-Teller (BET) method. The BET surface area measurement showed that the ZnO obtained has a surface area of 27.8 m2/gram.
- The nano zinc oxide (n-ZnO) together with titanium dioxide (TiO2) as the main pigment was used to formulate an acrylic water-based paint. The formulation was named “n-ZnO Formulation”. The weight of the TiO2 present in this formulation was 70% of that present in the Standard Formulation described below. A comparative acrylic water-based paint formulation based on TiO2 pigments alone was made. This formulation was named “Standard Formulation”.
- When 30% of the required TiO2 was replaced in the “n-ZnO Formulation” with nano zinc oxide, there was a decrease in the total pigment volume. This decrease in pigment volume was compensated by increasing the amount of silica and/or talc to keep the pigment volume concentration the same in the formulations shown in Table 3 below.
- Contrast Ratio was measured using the ZEHNTNER Reflectometer, (Zehntner Testing Instruments, Switzerland). Accelerated storage studies were made by storing the paint at 60° C. for fourteen days and assessing the paint appearance visually for any cake formation, hard settlement and paint flow.
-
TABLE 3 Paint formulation using Nano-ZnO Standard n-ZnO Formulation Formulation No. Materials (in grams) (in grams) 1. Thickener-1 (Aquaflow ™ 0.20 0.20 NHS 300, obtained from Hercules Inc., Delaware, USA) 2. Thickener-2 (Aquaflow ™ 0.10 0.10 NHS 300, obtained from Hercules Inc., Delaware, USA) 3. Dispersing agent (Coatex 0.50 0.50 P 90, obtained from Coatex Inc, Arkema, South Carolina, USA) 4. Defoamer (Tego ® Foamex 0.45 0.45 825, obtained from Evonik Industries, Germany) 5. Water 30.58 28.00 6. n-ZnO -NA- 1.50 7. Titanium dioxide 27.00 18.90 8. Calcium Carbonate 20.50 20.50 9. Silica 0.98 5.00 10. Fumed Silica 0.98 0.98 11. Acrylic Resin emulsion 43.5 43.5 (UCAR ™ 362, obtained from The Dow Chemical Company, California, USA) 12. ROPAQUE ™ emulsion 19.5 19.5 (obtained from The Dow Chemical Company, California, USA) 13. Texanol (obtained from 2.76 2.76 Eastman Chemical Company, Tennessee, USA) 14. 2-Amino-2-methyl-1- 0.15 0.15 propanol + 5% water (AMP ™-95 obtained from The Dow Chemical Company, California, USA) Contrast Ratio (Opacity) 91.83 93.81 (%) Accelerated storage test Pass-- Fails-paint homogeneous solidified Paint with into thick slightly mass reduced flow - As can be seen from Table 3, the incorporation of nano zinc oxide, while increasing the opacity of the paint formulation, caused the paint formulation to gel and become unstable.
- The disclosed composition advantageously enhances the stability of a paint formulation without depriving the paint formulations from being economically feasible to produce or affecting the opacity of the paint formulation.
- Advantageously, the disclosed composition permits a lower amount of expensive raw material required in paint formulations without depriving the paint formulations of the properties required. In embodiments, the composite of the present disclosure can be used as a partial replacement for the relatively more expensive titanium dioxide pigment in paint formulations. Furthermore, the disclosed composition possesses improved durability against the natural elements.
- Advantageously, the disclosed composite confers anti-bacterial properties to the composition.
- Advantageously, the disclosed composite improves the ultraviolet resistance of the composition, thereby conferring durability to the composition.
- Advantageously, the disclosed composite does not leach out of the composition.
- Advantageously, in embodiments, the disclosed composite of the present disclosure can be used as partial replacement for conventional ZnO in the vulcanization of rubber.
- In embodiments, the disclosed composite of the present disclosure can be used as a wide band width semiconductor in certain electronic applications.
- In embodiments, the disclosed composite of the present disclosure can also be used to improve abrasion and wear resistance in polymer composites whether alone or in combination with other nanomaterials such as clay.
- In embodiments, the disclosed composite of the present disclosure can be dispersed in organic solvents and polymers to improve the durability of organic polymer composites to the natural elements.
- It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.
Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/139,532 US20210163753A1 (en) | 2013-09-13 | 2020-12-31 | Composite pigments |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1316316.7A GB2518202B (en) | 2013-09-13 | 2013-09-13 | Composite pigments |
GB1316316.7 | 2013-09-13 | ||
PCT/SG2014/000432 WO2015038073A1 (en) | 2013-09-13 | 2014-09-12 | Composite pigments |
US201615021558A | 2016-03-11 | 2016-03-11 | |
US17/139,532 US20210163753A1 (en) | 2013-09-13 | 2020-12-31 | Composite pigments |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/021,558 Division US10899931B2 (en) | 2013-09-13 | 2014-09-12 | Composite pigments |
PCT/SG2014/000432 Division WO2015038073A1 (en) | 2013-09-13 | 2014-09-12 | Composite pigments |
Publications (1)
Publication Number | Publication Date |
---|---|
US20210163753A1 true US20210163753A1 (en) | 2021-06-03 |
Family
ID=49552616
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/021,558 Active US10899931B2 (en) | 2013-09-13 | 2014-09-12 | Composite pigments |
US17/139,532 Abandoned US20210163753A1 (en) | 2013-09-13 | 2020-12-31 | Composite pigments |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/021,558 Active US10899931B2 (en) | 2013-09-13 | 2014-09-12 | Composite pigments |
Country Status (21)
Country | Link |
---|---|
US (2) | US10899931B2 (en) |
EP (1) | EP3044256A4 (en) |
JP (3) | JP2016534212A (en) |
KR (1) | KR102128644B1 (en) |
CN (1) | CN105722903B (en) |
AP (1) | AP2016009138A0 (en) |
AU (2) | AU2014319022A1 (en) |
BR (1) | BR112016005534B1 (en) |
CA (1) | CA2924226C (en) |
CL (1) | CL2016000563A1 (en) |
EA (1) | EA039844B1 (en) |
GB (1) | GB2518202B (en) |
IL (1) | IL244558B (en) |
MX (1) | MX2016003275A (en) |
MY (1) | MY172528A (en) |
NZ (1) | NZ718968A (en) |
PH (1) | PH12016500483A1 (en) |
SA (1) | SA516370723B1 (en) |
SG (1) | SG11201601677QA (en) |
WO (1) | WO2015038073A1 (en) |
ZA (1) | ZA201602475B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11202738B2 (en) * | 2015-10-05 | 2021-12-21 | M. Technique Co., Ltd. | Metal oxide particles and method of producing the same |
US20170267877A1 (en) | 2016-03-16 | 2017-09-21 | The Sherwin-Williams Company | Opacifying clusters for use in paint compositions |
WO2018079486A1 (en) * | 2016-10-24 | 2018-05-03 | 石原産業株式会社 | Composite pigment and production method thereof, paint composition containing composite pigment, and coating film |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060167138A1 (en) * | 2002-06-05 | 2006-07-27 | Showa Denko K.K. | Powder comprising silica-coated zinc oxide, organic polymer composition containing the powder and shaped article thereof |
US20120097068A1 (en) * | 2009-06-24 | 2012-04-26 | Base Se | Modified zno nanoparticles |
US20140256849A1 (en) * | 2013-03-11 | 2014-09-11 | Ppg Industries Ohio, Inc. | Silicate enclosed pigment particles |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2882178A (en) * | 1958-01-16 | 1959-04-14 | Nat Lead Co | Composite antimony oxide-silica pigment and process of manufacture |
GB1532521A (en) * | 1976-04-02 | 1978-11-15 | Laporte Au Ltd | Pigments |
JPS63199275A (en) | 1987-02-13 | 1988-08-17 | Ube Ind Ltd | White paint for painting |
US5203916A (en) * | 1992-04-10 | 1993-04-20 | Kerr-Mcgee Chemical Corporation | Titanium dioxide pigment and method of preparation |
US5389140A (en) * | 1992-10-30 | 1995-02-14 | Kansai Paint Co., Ltd. | Electrodeposition paint composition |
JPH07328421A (en) * | 1994-06-06 | 1995-12-19 | Nippon Shokubai Co Ltd | Inorganic compound fine particle, its production and its use |
US6200680B1 (en) * | 1994-06-06 | 2001-03-13 | Nippon Shokubai Co., Ltd. | Fine zinc oxide particles, process for producing the same, and use thereof |
JP3010247B2 (en) * | 1994-06-10 | 2000-02-21 | 工業技術院長 | Plate-like alumina pigment and method for producing the same |
EP0988853B1 (en) | 1997-04-18 | 2012-10-24 | Showa Denko K.K. | Cosmetic preparation, silica-coated metal oxide powder, and process for producing the same |
JP2002121494A (en) * | 2000-10-19 | 2002-04-23 | Nippon Paint Co Ltd | Brilliant coating composition, method for forming coating film and coated product |
JP2002192067A (en) * | 2000-12-28 | 2002-07-10 | Nippon Paint Co Ltd | Brilliant coating film forming method and coated material |
JP2003055573A (en) * | 2001-08-14 | 2003-02-26 | Nippon Shikizai Inc | Laminate type coherent spheroidal pigment and cosmetic formulating the same |
JP3986304B2 (en) * | 2001-12-06 | 2007-10-03 | 株式会社日本色材工業研究所 | Laminated interference UV shielding pigment and cosmetics containing the same |
DE10259246A1 (en) | 2002-12-17 | 2004-07-01 | Merck Patent Gmbh | Inorganic spherical absorption pigments |
US6866711B2 (en) * | 2003-01-17 | 2005-03-15 | Fitzgerald Alphanso Sinclair | Composite pigment composition containing silica |
JP2005199261A (en) * | 2003-12-17 | 2005-07-28 | Fujikura Kasei Co Ltd | Photocatalyst composite material, coating composition comprising photocatalyst and self-cleaning type coating film |
US7498081B2 (en) * | 2005-03-02 | 2009-03-03 | Thw Shwphwed Color Company | Core-shell composite inorganic pigments and method of preparation for crystallizable glass frit compositions |
JP2007261082A (en) | 2006-03-28 | 2007-10-11 | Matsushita Electric Works Ltd | Coating article with visual contamination reduced |
DE102006038518A1 (en) * | 2006-08-17 | 2008-02-21 | Evonik Degussa Gmbh | Enveloped zinc oxide particles |
TW200846027A (en) * | 2006-12-20 | 2008-12-01 | Avon Prod Inc | Nanocomposite pigments in a topical cosmetic application |
JP5547526B2 (en) * | 2009-05-19 | 2014-07-16 | 関西ペイント株式会社 | Coating composition, coating film forming method and coating film structure |
CN102471605B (en) * | 2009-08-04 | 2015-06-17 | 莱雅公司 | Composite pigment and method for preparation thereof |
JP5455501B2 (en) * | 2009-08-07 | 2014-03-26 | 日揮触媒化成株式会社 | Dispersion of core-shell composite oxide fine particles, method for producing the dispersion, coating composition containing the core-shell composite oxide fine particles, curable coating, and substrate with curable coating |
DE102009051171A1 (en) | 2009-10-29 | 2011-05-05 | Merck Patent Gmbh | pigments |
CN101880501B (en) * | 2010-07-09 | 2012-04-18 | 重庆航利实业有限责任公司 | Nano ZnO/SiO2 sol modified self-cleaning silicone-acrylic exterior wall insulating mould coating |
JP2012021089A (en) * | 2010-07-15 | 2012-02-02 | Kansai Paint Co Ltd | Coating composition and method for forming coated film |
JP5713668B2 (en) | 2010-12-28 | 2015-05-07 | 日揮触媒化成株式会社 | Hard coat layer film forming coating composition |
JP5642535B2 (en) | 2010-12-28 | 2014-12-17 | 日揮触媒化成株式会社 | Novel silica-based hollow fine particles, base material with transparent film, and paint for forming transparent film |
EP2872106B2 (en) * | 2012-07-13 | 2023-08-02 | L'oreal | Composite pigment and method for preparing the same |
JP6016548B2 (en) * | 2012-09-19 | 2016-10-26 | 日揮触媒化成株式会社 | Coating liquid for forming transparent film and substrate with transparent film |
CN103242821B (en) | 2013-05-21 | 2014-12-24 | 中国科学院上海硅酸盐研究所 | Thermochromic composite powder with core-shell structure and preparation method of powder |
CN103436111B (en) * | 2013-07-29 | 2017-11-10 | 复旦大学 | A kind of preparation method of the water-based ultraviolet shielded coating based on ZnO quantum dot |
-
2013
- 2013-09-13 GB GB1316316.7A patent/GB2518202B/en not_active Expired - Fee Related
-
2014
- 2014-09-12 SG SG11201601677QA patent/SG11201601677QA/en unknown
- 2014-09-12 EA EA201690586A patent/EA039844B1/en unknown
- 2014-09-12 MX MX2016003275A patent/MX2016003275A/en unknown
- 2014-09-12 CN CN201480049554.9A patent/CN105722903B/en active Active
- 2014-09-12 BR BR112016005534-9A patent/BR112016005534B1/en active IP Right Grant
- 2014-09-12 MY MYPI2016000461A patent/MY172528A/en unknown
- 2014-09-12 KR KR1020167009703A patent/KR102128644B1/en active IP Right Grant
- 2014-09-12 EP EP14844848.3A patent/EP3044256A4/en active Pending
- 2014-09-12 AU AU2014319022A patent/AU2014319022A1/en not_active Abandoned
- 2014-09-12 CA CA2924226A patent/CA2924226C/en active Active
- 2014-09-12 JP JP2016541937A patent/JP2016534212A/en active Pending
- 2014-09-12 WO PCT/SG2014/000432 patent/WO2015038073A1/en active Application Filing
- 2014-09-12 US US15/021,558 patent/US10899931B2/en active Active
- 2014-09-12 AP AP2016009138A patent/AP2016009138A0/en unknown
- 2014-09-12 NZ NZ718968A patent/NZ718968A/en not_active IP Right Cessation
-
2016
- 2016-03-10 CL CL2016000563A patent/CL2016000563A1/en unknown
- 2016-03-11 PH PH12016500483A patent/PH12016500483A1/en unknown
- 2016-03-12 SA SA516370723A patent/SA516370723B1/en unknown
- 2016-03-13 IL IL244558A patent/IL244558B/en active IP Right Grant
- 2016-04-12 ZA ZA2016/02475A patent/ZA201602475B/en unknown
-
2018
- 2018-02-20 AU AU2018201207A patent/AU2018201207B2/en not_active Ceased
- 2018-12-06 JP JP2018228795A patent/JP2019077874A/en active Pending
-
2020
- 2020-12-31 US US17/139,532 patent/US20210163753A1/en not_active Abandoned
-
2022
- 2022-05-02 JP JP2022075955A patent/JP2022110022A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060167138A1 (en) * | 2002-06-05 | 2006-07-27 | Showa Denko K.K. | Powder comprising silica-coated zinc oxide, organic polymer composition containing the powder and shaped article thereof |
US20120097068A1 (en) * | 2009-06-24 | 2012-04-26 | Base Se | Modified zno nanoparticles |
US20140256849A1 (en) * | 2013-03-11 | 2014-09-11 | Ppg Industries Ohio, Inc. | Silicate enclosed pigment particles |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20210163753A1 (en) | Composite pigments | |
KR101859238B1 (en) | Effect pigments | |
EP2237899B1 (en) | Photocatalytic coating compositions | |
KR102431889B1 (en) | Composite pigment and manufacturing method thereof, paint composition containing composite pigment, and coating film | |
AU2012275783B2 (en) | Treated inorganic particle | |
JP4801617B2 (en) | Conductive zinc oxide particles and method for producing the same | |
TWI682900B (en) | Titanium dioxide pigment and method for producing the same, and composition containing the same | |
EP3040383A1 (en) | Black pigment having infrared-reflecting properties, and paint and resin composition that use said black pigment having infrared-reflecting properties | |
JP5455148B2 (en) | Infrared reflective composite black pigment, method for producing the infrared reflective composite black pigment, paint and resin composition using the infrared reflective composite black pigment | |
JP5258447B2 (en) | Dispersion of titanium oxide composite particles and method for producing the dispersion | |
JP6732781B2 (en) | Aluminum hydroxide-containing composite pigment and method for producing the same | |
WO2010143068A1 (en) | Mineral blends for low-titania coatings | |
WO2015138901A1 (en) | Agglomerated mineral composites |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SHAYONANO SINGAPORE PTE LTD., SINGAPORE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PATEL, MAHESH DAHYABHAI;NITHIANANDAM, VARADALAMBEDU SRINIVASAN;REEL/FRAME:054788/0551 Effective date: 20160520 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: APPLICATION DISPATCHED FROM PREEXAM, NOT YET DOCKETED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: EX PARTE QUAYLE ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE |