USRE41858E1 - Pearlescent pigment for water-borne surface-coating systems - Google Patents
Pearlescent pigment for water-borne surface-coating systems Download PDFInfo
- Publication number
- USRE41858E1 USRE41858E1 US12/574,739 US57473909A USRE41858E US RE41858 E1 USRE41858 E1 US RE41858E1 US 57473909 A US57473909 A US 57473909A US RE41858 E USRE41858 E US RE41858E
- Authority
- US
- United States
- Prior art keywords
- pigment
- top layer
- metal oxide
- metal
- titanium dioxide
- 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.)
- Expired - Lifetime
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 110
- 239000011248 coating agent Substances 0.000 title claims description 30
- 238000000576 coating method Methods 0.000 title claims description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 68
- -1 metal oxide hydrates Chemical class 0.000 claims abstract description 62
- 230000008878 coupling Effects 0.000 claims abstract description 47
- 238000010168 coupling process Methods 0.000 claims abstract description 47
- 238000005859 coupling reaction Methods 0.000 claims abstract description 47
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 46
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 45
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 37
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 150000004677 hydrates Chemical class 0.000 claims abstract description 5
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 239000004408 titanium dioxide Substances 0.000 claims description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 28
- 229910000077 silane Inorganic materials 0.000 claims description 28
- 239000010445 mica Substances 0.000 claims description 24
- 229910052618 mica group Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 8
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 66
- 150000004756 silanes Chemical class 0.000 abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 90
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 53
- 239000000725 suspension Substances 0.000 description 43
- 238000003756 stirring Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 18
- 230000008859 change Effects 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 16
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 11
- 206010042674 Swelling Diseases 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008961 swelling Effects 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 8
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000007793 ph indicator Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 241000197192 Bulla gouldiana Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- GRQOVJIJVUKVIQ-UHFFFAOYSA-M O.O.O.O.O.O.O.O.[Cl-].[O-2].[Zr+4] Chemical compound O.O.O.O.O.O.O.O.[Cl-].[O-2].[Zr+4] GRQOVJIJVUKVIQ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000005371 silicon functional group Chemical group 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RDIAXPJGEFJVMM-UHFFFAOYSA-K [H]O1[Al](O)OC(CC)O[Zr]1(O)O Chemical compound [H]O1[Al](O)OC(CC)O[Zr]1(O)O RDIAXPJGEFJVMM-UHFFFAOYSA-K 0.000 description 1
- ZHVGFVZCBNBRQQ-UHFFFAOYSA-M [O-2].[Cl-].[Zr+4] Chemical compound [O-2].[Cl-].[Zr+4] ZHVGFVZCBNBRQQ-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- KKFPIBHAPSRIPB-UHFFFAOYSA-N cerium(3+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Ce+3].[Ce+3] KKFPIBHAPSRIPB-UHFFFAOYSA-N 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940056960 melamin Drugs 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- 238000009736 wetting Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
-
- 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
- C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- 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
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
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- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/401—Inorganic protective coating
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- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/402—Organic protective coating
- C09C2200/407—Organosilicon materials, e.g. silanes, silicones
- C09C2200/408—Organosilicon materials, e.g. silanes, silicones comprising additional functional groups, e.g. –NH2, -C=C- or -SO3
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- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/409—Mixed inorganic-organic coating
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- 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
- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/10—Wet methods, e.g. co-precipitation
Definitions
- the invention relates to surface-modified pearlescent pigments for water-borne surface-coating systems.
- titanium dioxide particles present as the pigment component in a surface-coating composition cause oxidative decomposition of the polymer on exposure to ultra-violet rays and moisture, known as whitening.
- EP-A-0 268 918 describes a weathering-resistant pearlescent pigment having a hydrated zirconium oxide coating on the titanium dioxide base pigment, this coating being obtained by hydrolysis of a zirconium salt in the presence of a hypophosphite.
- EP-A-0 342 533 describes a weathering-resistant pearlescent pigment having, on the titanium dioxide base pigment, a top layer comprising hydrated zirconium oxide obtained by hydrolysis in the presence of a hypophosphite, and a hydrated metal oxide.
- the metal oxide can be cobalt oxide, manganese oxide or cerium oxide.
- modified pearlescent pigments have adequate dispersibility and weathering resistance in non-aqueous surface-coating systems. However, they are not suitable for use in water-thinnable surface-coating systems, since they cause the formation of microfine bubbles in the coating film which significantly increases light scattering and thus adversely affects gloss and color. In addition, the distinctness of image (DOI) is greatly reduced and the regeneration capacity of the coating film is impaired.
- the organofunctional silanes have the following basic structure Y—(CH 2 ) n —SiX 3 , where Y is an organofunctional group, for example an NH 2 group, which is rigidly bonded to the silicon via a carbon chain.
- Y is an organofunctional group, for example an NH 2 group, which is rigidly bonded to the silicon via a carbon chain.
- X is referred to as a silicon-functional group.
- These are generally alkoxy groups, which, after hydrolysis, react with active sites of an inorganic substrate or with other silicon compounds by condensation and thus form stable bonds.
- An object of the present invention is therefore to provide a pearlescent pigment having excellent weathering resistance which is suitable for various, chemically different water-thinnable surface coating systems.
- a pearlescent pigment based on a metal oxide-coated, platelet-shaped substrate and a top layer on the metal oxide layer, where the top layer comprises silicon dioxide, at least one further metal oxide or metal oxide hydrate and at least one organic coupling reagent.
- the object is furthermore achieved according to the present invention by a process for the preparation of a pearlescent pigment based on a metal oxide-coated, platelet-shaped substrate and a top layer on the metal oxide layer, in which the metal oxide-coated substrate is suspended in water, in a first step silicic acid is deposited by adding a water-soluble silicate at a pH from 6 to 9, then in a second step, after addition of one or more water-soluble metal salts at a pH from 3 to 7 and heating to from 30° to 100° C., preferably from 40° to 75° C., the metal hydroxides or metal oxide hydrates are partly deposited, in a third step at least one coupling reagent is added and is hydrolyzed at a pH of from 3 to 4, and finally in a fourth step the part of the metals remaining in solution is deposited as hydroxides or oxide hydrates together with the coupling reagent at a pH of from 4 to 8.5, and the pigment is subsequently dried at from 80° to 160° C.,
- the invention furthermore relates to the use of the pigments according to the invention for pigmenting surface-coating compositions or plastics.
- the substrates used are pigments which comprise a platelet-shaped material, for example mica, kaolin or glass, and one or more metal oxide layers deposited thereon.
- the metal oxide layer can comprise, for example, titanium dioxide, titanium dioxide mixed with iron (III) oxide, iron (III) oxide, chromium oxide, zirconium dioxide, tin dioxide or zinc oxide. Pigments of this type are exemplified by those commercially available under the name Iriodin® (manufacturer: E. MERCK, Darmstadt).
- the proportion of the total amount of pigment made up by the top layer on the metal oxide coated substrate is from 4 to 20% by weight, preferably from 4 to 10% by weight. Of this, from 1 to 3% by weight is made up by silicon dioxide, from 1 to 5% by weight by further metal oxides and from 2 to 12% by weight by the coupling reagent.
- the preferred further metal oxides present in the top layer are aluminum oxide, cerium (III) oxide and zirconium dioxide.
- the coupling reagents used are compounds which comprise one or more central atoms and, bonded thereto, hydrolyzable groups and one or more organic radicals carrying functional groups.
- the central atoms can be silicon, aluminum, zirconium or titanium.
- Suitable coupling reagents are zirconium aluminates of the following structure in which X is —NH 2 , —COOH, —COO ⁇ , hydroxyphenyl, methacrylate, carboxyphenyl, alkyl, mercapto, phenyl, —H, vinyl, styryl, melamin, epoxy, aryl or alkyl, and R is —(CH 2 ) n — in which n can be from 0 to 12.
- the dotted line in the formula indicates the fourth electron pair of the ring carbon atom used to bond the two oxygen atoms.
- the triangular bonds in the formula indicate that the oxygen atom has pseudo-bonding to the Zr atom and Al atom, as well as to the hydrogen.
- zirconium aluminates are commercially available under the trade name MANCHEM® (manufacturer: Manchem Limited, Great Britain).
- Suitable coupling reagents are metal acid esters of the following structure M n (OR) N wherein
- metal acid esters are acrylate-functional and methacrylamide-functional titanates and methacrylamide-functional zirconates.
- organofunctional silanes according to the invention can be employed as coupling reagents, the following compounds being particularly suitable:
- the object of the silicon-functional group is to form hydrogen bridge bonds and chemical bonds to the OH groups of the pigment surface after hydrolysis. This gives a stable bond between the silane and pigment surface.
- the object of the organofunctional group of the silane is to form bonds to the polymer of the water-borne surface-coating composition.
- the suitable coupling reagent-modified pigment it is incumbent on the person skilled in the art to select the suitable coupling reagent-modified pigment to match the polymer of the water-borne surface-coating composition. If polyester is used as the polymer in the water-borne system, the pigment should be modified by means of a coupling reagent which contains a methacrylate group as the organo-functional group. If urethane is used as the polymer, an amino-functional coupling reagent should be used to modify the pigment.
- the pigments according to the invention can be matched to the various water-borne surface-coating systems.
- the pigments according to the invention are prepared by, in a first step, depositing from 0.1 to 10% by weight, preferably from 0.5 to 3% by weight, of silicon dioxide on the metal oxide layer of the substrate (base pigment). To this end, an aqueous, from 1 to 35%, preferably from 5 to 20%, suspension of the base pigment is treated at a pH from 6 to 9 with a dilute sodium silicate solution. The pH is kept constant by addition of hydrochloric acid, all the stated pH values being determined with the aid of indicator paper.
- aqueous salt solutions or solid salts of the metals cerium, aluminum or zirconium, or mixtures thereof, in a concentration of from 1 to 4% by weight, based on oxide, are added to an aqueous suspension of the substrate coated in step 1 in the presence of a soluble sulfate, the pH is kept constant at from 3 to 5, and the suspension is heated at from 30° to 100° C., preferably at from 40° to 75° C., with stirring, for from 5 minutes to 4 hours, preferably for from 30 minutes to 2 hours.
- a third step from 1 to 20% by weight, preferably from 2 to 12% by weight, of coupling reagent, based on the pigment employed, are then added, the suspension is stirred for from 5 minutes to 4 hours, preferably for from 30 minutes to 2 hours, at a pH from 3 to 5, and the pH is then adjusted to a value of from 5 to 8 over the course of from 5 minutes to 4 hours, preferably from 30 minutes to 2 hours, during which the suspension is kept at a temperature of from 30° to 100° C., preferably from 40° to 75° C.
- the pigment is subsequently separated off, washed until free of salt and dried at from 80° to 180° C., preferably at from 120° to 160° C.
- the neutral-color pigments obtained in this way have very good weathering resistance, which is confirmed by the test results carried out below.
- the pigment is on the one hand readily free-flowing and on the other hand has very good suitability for water-thinnable surface-coating systems, in particular automotive paint systems, with respect to dispersibility, stability, coloristic properties, microbubble formation, swelling and gloss.
- the pigment samples were incorporated into a plastic matrix, and the extent of reduction of Pb 2+ to Pb was determined visually.
- the grey coloration was assessed in accordance with ISO 105, part A 02 (corresponds to DIN 54 001).
- the test scale extends from 5 (very good) to 1 (very poor).
- the pigment samples were incorporated into a conventional surface-coating system, and the test samples were prepared by spray application.
- the testing was carried out in a one-coat system after 16 hours at 66° C. and after 20 hours at 80° C.
- the grey coloration was assessed visually in accordance with ISO 105, part A 02 (corresponds to DIN 54 001) 24 hours after completion of the exposure.
- the assessment scale extends from 5 (very good) to 1 (very poor).
- the pigment samples were incorporated into three different water-borne surface-coating systems (A, B, C), and the test samples were prepared by spray application.
- the test was carried out in accordance with DIN 50 017 (condensation water/constant climate) one hour after completion of the exposure.
- the assessment of the bubble frequency was carried out visually in accordance with DIN 53 209. “m” indicates the frequency of bubbles per unit area, and “g” denotes the bubble size.
- the assessment scale extends from 0 (very good) to 5 (very poor), i.e., the reverse of the two test methods above.
- the swelling process was assessed visually in accordance with DIN 53 230, Table 2.
- the number 0 means “unchanged” and the number 5 means “very considerably changed”.
- Table 1 shows the test results for the pigments prepared in accordance with Examples 1 to 20 as measured by the test methods described above.
- the zero sample shown at the end comprised the pure water-borne surface-coating systems without pigment.
- the zero sample shows that the pure water-borne surface-coating systems also have slight swellings.
- Table 2 shows, for comparison, the test results for the conventional pigments used in Comparative Examples 1 to 4.
- Comparative Examples 1 and 2 Iriodin® 9225 Rutile Pearlescent Blue, a titanium dioxide coated mica pigment, was employed. In Comparative Example 2, it was provided with an additional coating of compounds of chromium and manganese as described in EP 0 104 516, and in Comparative Example 1 it was provided with an additional coating of zirconium oxide hydrate, cerium oxide hydrate and an epoxy silane as described in EP 0 342 533.
- Comparative Examples 3 and 4 Iriodin® 9504 Red, an iron(III) oxide-coated mica pigment, was used. In Comparative Example 3 it was provided with an additional coating as described in EP 0 342 533, and in Comparative Example 4 it was provided with an additional coating as described in EP 0 104 516.
- the comparative examples show that the surface-coating systems containing the pigments according to the invention have significantly better swelling behavior than those containing conventional pigments (see water-borne surface-coating system B, Examples 10, 11, and 13).
- Iriodin® 504 Red iron(III) oxide-coated mica pigment from E. Merck, Darmstadt
- demineralized water 100 g of Iriodin® 504 Red (iron(III) oxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous, stirring.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 2.7 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 1.10 g of cerium(III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution.
- the metal hydroxides or metal oxide hydrates, silanes of various functionality and zirconium aluminate are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid.
- the mixture is stirred at 75° C. for a further 2 hours, during which the silanes and the zirconium aluminate coupling reagent are fully hydrolyzed and become reactive. The pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution.
- the metal hydroxides or metal oxide hydrates, silanes of various functionality and zirconium aluminate are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the silane and the zirconium aluminate coupling reagent are fully hydrolyzed and become reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, the silane and zirconium aluminate are coprecipitated completely. The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the zirconium aluminate coupling reagent is fully hydrolyzed and becomes reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, and the zirconium aluminate are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- Manchem A aminozirconium aluminate solution from Rhône Poulenc Chemicals
- the mixture is stirred at 75° C. for a further 2 hours, during which the zirconium aluminate coupling reagent is fully hydrolyzed and becomes reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, and zirconium aluminate are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the zirconium aluminate coupling reagent is fully hydrolyzed and becomes reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, and zirconium aluminate are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours. During this addition the silanes are fully hydrolyzed and become reactive. The pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Example 1 100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
- the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive.
- the pH does not change.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Iriodin® 504 Red iron (III) oxide-coated mica pigment from E. Merck, Darmstadt
- demineralized water 100 g of Iriodin® 504 Red (iron (III) oxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 5.4 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5 hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- 2.70 g of sodium sulfate, 4.60 g of aluminum chloride hexahydrate and 1.10 of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Iriodin® 504 Red iron (III) oxide-coated mica pigment from E. Merck, Darmstadt
- demineralized water 100 g of Iriodin® 504 Red (iron (III) oxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 8.1 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- 4.05 g of sodium sulfate, 6.90 g of aluminum chloride hexahydrate and 1.10 g of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- Iriodin® 225 Rutile Piglescent Blue titanium dioxide-coated mica pigment from E. Merck, Darmstadt
- demineralized water 100 g of Iriodin® 225 Rutile (Pearlescent Blue titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 2.7 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 1.70 g of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineratized water until salt-free and dried at 140° C. for about 16 hours.
- Iriodin® 225 Rutile Piglescent Blue titanium dioxide-coated mica pigment from E. Merck, Darmstadt
- demineralized water 100 g of Iriodin® 225 Rutile (Pearlescent Blue titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 2.7 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 2.25 g of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 2.7 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5 hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 2.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 2.7 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture then adjusted 40° C. for a further 15 minutes.
- the pH is adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is-stirred at 40° C. for a further 15 minutes.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 2.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 40 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
- the pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
- a solution of 2.7 ml of sodium water glass (370 g of SiO 2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension.
- the pH is kept constant by means of 2.5% hydrochloric acid.
- the mixture is stirred at 40° C. for a further 15 minutes.
- the pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
- the mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 2.3.
- the metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
- the pH is subsequently adjusted to 8.0 very slowly over the course of 25 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
- the mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
- the product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
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Abstract
A pearlescent pigment based on a metal oxide-coated, platelet-shaped substrate and a top layer on the metal oxide layer, where the top layer comprises silicon dioxide, at least one further metal hydroxide or metal oxide hydrate and at least one organic coupling reagent. The further metal hydroxides or metal oxide hydrates are hydroxides or oxide hydrates of cerium, aluminum or zirconium, or mixtures thereof. The coupling reagents employed are organofunctional silanes, zirconium aluminates or metal acid esters.
Description
The invention relates to surface-modified pearlescent pigments for water-borne surface-coating systems.
It is known that titanium dioxide particles present as the pigment component in a surface-coating composition cause oxidative decomposition of the polymer on exposure to ultra-violet rays and moisture, known as whitening. In order to suppress this effect of titanium dioxide, it has been proposed to coat or dope titanium dioxide with compounds of chromium, silicon, aluminum, zinc, phosphorus or zirconium.
EP-A-0 268 918 describes a weathering-resistant pearlescent pigment having a hydrated zirconium oxide coating on the titanium dioxide base pigment, this coating being obtained by hydrolysis of a zirconium salt in the presence of a hypophosphite.
EP-A-0 342 533 describes a weathering-resistant pearlescent pigment having, on the titanium dioxide base pigment, a top layer comprising hydrated zirconium oxide obtained by hydrolysis in the presence of a hypophosphite, and a hydrated metal oxide. The metal oxide can be cobalt oxide, manganese oxide or cerium oxide.
These modified pearlescent pigments have adequate dispersibility and weathering resistance in non-aqueous surface-coating systems. However, they are not suitable for use in water-thinnable surface-coating systems, since they cause the formation of microfine bubbles in the coating film which significantly increases light scattering and thus adversely affects gloss and color. In addition, the distinctness of image (DOI) is greatly reduced and the regeneration capacity of the coating film is impaired.
The Hüls AG company brochure “Dynasylan®-Anwendungen yon organofunktionellen Silanen” [Dynasylan®-Applications of Organofunctional Silanes] discloses silanes as coupling agents between inorganic materials (glass, minerals and metal) and organic polymers (thermosets, thermoplastics and elastomers). In a composite material comprising an inorganic substrate and a polymer, they improve the adhesion and thus the mechanical properties of the composite and, simultaneously, as surface modifiers, hydrophobicize the surface of the substrate and thus improve the wetting by the polymer.
The organofunctional silanes have the following basic structure
Y—(CH2)n—SiX3,
where Y is an organofunctional group, for example an NH2 group, which is rigidly bonded to the silicon via a carbon chain. X is referred to as a silicon-functional group. These are generally alkoxy groups, which, after hydrolysis, react with active sites of an inorganic substrate or with other silicon compounds by condensation and thus form stable bonds.
Y—(CH2)n—SiX3,
where Y is an organofunctional group, for example an NH2 group, which is rigidly bonded to the silicon via a carbon chain. X is referred to as a silicon-functional group. These are generally alkoxy groups, which, after hydrolysis, react with active sites of an inorganic substrate or with other silicon compounds by condensation and thus form stable bonds.
Attempts to modify the surface of pearlescent pigments with the aid of these organofunctional silanes in order to improve their weathering resistance and to make them suitable for water-thinnable surface-coating systems have given unsatisfactory results. The strength of the bond between the silane and the surface of the substrate is limited. Mechanical stress or weathering effects, as occur, for example, in an automotive paint, break the bond. A further disadvantage is that the coverage of the substrate surface by the silane is incomplete.
An object of the present invention is therefore to provide a pearlescent pigment having excellent weathering resistance which is suitable for various, chemically different water-thinnable surface coating systems.
Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.
This object is achieved according to the present invention by a pearlescent pigment based on a metal oxide-coated, platelet-shaped substrate and a top layer on the metal oxide layer, where the top layer comprises silicon dioxide, at least one further metal oxide or metal oxide hydrate and at least one organic coupling reagent. The object is furthermore achieved according to the present invention by a process for the preparation of a pearlescent pigment based on a metal oxide-coated, platelet-shaped substrate and a top layer on the metal oxide layer, in which the metal oxide-coated substrate is suspended in water, in a first step silicic acid is deposited by adding a water-soluble silicate at a pH from 6 to 9, then in a second step, after addition of one or more water-soluble metal salts at a pH from 3 to 7 and heating to from 30° to 100° C., preferably from 40° to 75° C., the metal hydroxides or metal oxide hydrates are partly deposited, in a third step at least one coupling reagent is added and is hydrolyzed at a pH of from 3 to 4, and finally in a fourth step the part of the metals remaining in solution is deposited as hydroxides or oxide hydrates together with the coupling reagent at a pH of from 4 to 8.5, and the pigment is subsequently dried at from 80° to 160° C., preferably at from 120° to 160° C.
The invention furthermore relates to the use of the pigments according to the invention for pigmenting surface-coating compositions or plastics.
The substrates used are pigments which comprise a platelet-shaped material, for example mica, kaolin or glass, and one or more metal oxide layers deposited thereon. The metal oxide layer can comprise, for example, titanium dioxide, titanium dioxide mixed with iron (III) oxide, iron (III) oxide, chromium oxide, zirconium dioxide, tin dioxide or zinc oxide. Pigments of this type are exemplified by those commercially available under the name Iriodin® (manufacturer: E. MERCK, Darmstadt).
The proportion of the total amount of pigment made up by the top layer on the metal oxide coated substrate is from 4 to 20% by weight, preferably from 4 to 10% by weight. Of this, from 1 to 3% by weight is made up by silicon dioxide, from 1 to 5% by weight by further metal oxides and from 2 to 12% by weight by the coupling reagent.
In addition to silicon dioxide, the preferred further metal oxides present in the top layer are aluminum oxide, cerium (III) oxide and zirconium dioxide.
The coupling reagents used are compounds which comprise one or more central atoms and, bonded thereto, hydrolyzable groups and one or more organic radicals carrying functional groups. The central atoms can be silicon, aluminum, zirconium or titanium.
Suitable coupling reagents are zirconium aluminates of the following structure
in which X is —NH2, —COOH, —COO−, hydroxyphenyl, methacrylate, carboxyphenyl, alkyl, mercapto, phenyl, —H, vinyl, styryl, melamin, epoxy, aryl or alkyl, and R is —(CH2)n— in which n can be from 0 to 12. The dotted line in the formula indicates the fourth electron pair of the ring carbon atom used to bond the two oxygen atoms. The triangular bonds in the formula indicate that the oxygen atom has pseudo-bonding to the Zr atom and Al atom, as well as to the hydrogen.
in which X is —NH2, —COOH, —COO−, hydroxyphenyl, methacrylate, carboxyphenyl, alkyl, mercapto, phenyl, —H, vinyl, styryl, melamin, epoxy, aryl or alkyl, and R is —(CH2)n— in which n can be from 0 to 12. The dotted line in the formula indicates the fourth electron pair of the ring carbon atom used to bond the two oxygen atoms. The triangular bonds in the formula indicate that the oxygen atom has pseudo-bonding to the Zr atom and Al atom, as well as to the hydrogen.
Particularly suitable zirconium aluminates are commercially available under the trade name MANCHEM® (manufacturer: Manchem Limited, Great Britain).
Other suitable coupling reagents are metal acid esters of the following structure
Mn(OR)N
wherein
Mn(OR)N
wherein
-
- M is Zr, Ti or Al
- n is the valence of the metal, and
- R is
- (i) alkyl of 1-12 carbon atoms or aryl,
- (ii) alkyl or aryl substituted by —N(alkyl)3, —NH(alkyl)2, —NH2(alkyl), —NH3, —N (aryl)3, —NH(aryl)2 or —NH2 (aryl), where aryl can be substituted by halogen, nitro, amino or hydrogen,
- (iii) —C-aryl or —C-alkyl.
Particularly suitable metal acid esters are commercially available, e.g., from Hüls AG (manufacturer).
Particularly suitable metal acid esters are acrylate-functional and methacrylamide-functional titanates and methacrylamide-functional zirconates.
Finally, organofunctional silanes according to the invention can be employed as coupling reagents, the following compounds being particularly suitable:
-
- Aminopropyltrimethoxysilane (Dynasilan AMMO)
- N-2-Aminoethyl-3-aminopropyltrimethoxysilane (Dynasilan DAMO)
- 3-Methacryloxypropyltrimethoxysilane (Dynasilan MEMO)
- 3-Glycidoxypropyltrimethoxysilane(Dynasilan GLYMO), which are marketed by Hüls AG.
The object of the silicon-functional group (methoxy group) is to form hydrogen bridge bonds and chemical bonds to the OH groups of the pigment surface after hydrolysis. This gives a stable bond between the silane and pigment surface. The object of the organofunctional group of the silane is to form bonds to the polymer of the water-borne surface-coating composition.
It is incumbent on the person skilled in the art to select the suitable coupling reagent-modified pigment to match the polymer of the water-borne surface-coating composition. If polyester is used as the polymer in the water-borne system, the pigment should be modified by means of a coupling reagent which contains a methacrylate group as the organo-functional group. If urethane is used as the polymer, an amino-functional coupling reagent should be used to modify the pigment.
By appropriate choice of the coupling reagents, the pigments according to the invention can be matched to the various water-borne surface-coating systems.
The pigments according to the invention are prepared by, in a first step, depositing from 0.1 to 10% by weight, preferably from 0.5 to 3% by weight, of silicon dioxide on the metal oxide layer of the substrate (base pigment). To this end, an aqueous, from 1 to 35%, preferably from 5 to 20%, suspension of the base pigment is treated at a pH from 6 to 9 with a dilute sodium silicate solution. The pH is kept constant by addition of hydrochloric acid, all the stated pH values being determined with the aid of indicator paper.
In a second step, after the pH has been adjusted to a value from 3 to 5, aqueous salt solutions or solid salts of the metals cerium, aluminum or zirconium, or mixtures thereof, in a concentration of from 1 to 4% by weight, based on oxide, are added to an aqueous suspension of the substrate coated in step 1 in the presence of a soluble sulfate, the pH is kept constant at from 3 to 5, and the suspension is heated at from 30° to 100° C., preferably at from 40° to 75° C., with stirring, for from 5 minutes to 4 hours, preferably for from 30 minutes to 2 hours.
Under these conditions, only some, a maximum of 50%, of the metal ions are precipitated as hydroxides or oxide hydrates.
In a third step, from 1 to 20% by weight, preferably from 2 to 12% by weight, of coupling reagent, based on the pigment employed, are then added, the suspension is stirred for from 5 minutes to 4 hours, preferably for from 30 minutes to 2 hours, at a pH from 3 to 5, and the pH is then adjusted to a value of from 5 to 8 over the course of from 5 minutes to 4 hours, preferably from 30 minutes to 2 hours, during which the suspension is kept at a temperature of from 30° to 100° C., preferably from 40° to 75° C.
Under these conditions, all the remaining metal ions are coprecipitated as hydroxides or oxide hydrates together with the coupling reagent.
The pigment is subsequently separated off, washed until free of salt and dried at from 80° to 180° C., preferably at from 120° to 160° C.
The neutral-color pigments obtained in this way have very good weathering resistance, which is confirmed by the test results carried out below. The pigment is on the one hand readily free-flowing and on the other hand has very good suitability for water-thinnable surface-coating systems, in particular automotive paint systems, with respect to dispersibility, stability, coloristic properties, microbubble formation, swelling and gloss.
The pigments according to the invention were tested by the 3 test methods below:
Photoactivity
The pigment samples were incorporated into a plastic matrix, and the extent of reduction of Pb2+ to Pb was determined visually. The grey coloration was assessed in accordance with ISO 105, part A 02 (corresponds to DIN 54 001). The test scale extends from 5 (very good) to 1 (very poor).
Water Immersion Test
The pigment samples were incorporated into a conventional surface-coating system, and the test samples were prepared by spray application. The testing was carried out in a one-coat system after 16 hours at 66° C. and after 20 hours at 80° C. The grey coloration was assessed visually in accordance with ISO 105, part A 02 (corresponds to DIN 54 001) 24 hours after completion of the exposure. The assessment scale extends from 5 (very good) to 1 (very poor).
The pigment samples were incorporated into three different water-borne surface-coating systems (A, B, C), and the test samples were prepared by spray application.
The test was carried out in accordance with DIN 50 017 (condensation water/constant climate) one hour after completion of the exposure. The assessment of the bubble frequency was carried out visually in accordance with DIN 53 209. “m” indicates the frequency of bubbles per unit area, and “g” denotes the bubble size. The assessment scale extends from 0 (very good) to 5 (very poor), i.e., the reverse of the two test methods above.
The swelling process was assessed visually in accordance with DIN 53 230, Table 2. In the relevant assessment scale, the number 0 means “unchanged” and the number 5 means “very considerably changed”.
Table 1 shows the test results for the pigments prepared in accordance with Examples 1 to 20 as measured by the test methods described above.
The zero sample shown at the end comprised the pure water-borne surface-coating systems without pigment. The zero sample shows that the pure water-borne surface-coating systems also have slight swellings.
TABLE 1 |
Test results for the pigments prepared in accordance with Examples 1 to 20 |
Condensation water test on water-thinnable | ||
Water immersion | surface-coating systems |
Photo- | test | A | B | C |
Example | activity | 16 h/66° C. | 20 h/80° C. | Bubbles | Swelling | Bubbles | Swelling | Bubbles | Swelling |
1 | 5 | 5 | 4-5 | m 0/g 0 | Q 0 | / | / | / | / |
2 | 3-4 | 4-5 | 3-4 | m 0/g 0 | Q 0 | m 0/g 0 | Q 3 | m 2/g 1 | Q 2-3 |
3 | 3-4 | 4-5 | 3-4 | / | / | m 0/g 0 | Q 2 | / | / |
4 | 3-4 | 4-5 | 4-5 | m 1/g 1 | Q 1 | m 0/g 0 | Q 3-4 | m 1/g 2 | Q 2-3 |
5 | 3-4 | 4-5 | 4 | m 3/g 1 | Q 0-1 | m 0/g 0 | Q 2-3 | m 0g 0 | Q 3 |
6 | 3-4 | 5 | 3-4 | / | / | / | / | m 4/g 1 | Q 2 |
7 | 3-4 | 5 | 4 | / | / | / | / | / | / |
8 | 3-4 | 5 | 3-4 | / | / | / | / | / | / |
9 | 3-4 | 5 | 4 | / | / | m 0/g 0 | Q 1 | m 0/g 0 | Q 3-4 |
10 | 3-4 | 5 | 4 | m 0/g 0 | Q 0-1 | m 0/g 0 | Q 1-2 | m 0/g 0 | Q 3-4 |
11 | 3-4 | 5 | 4 | m 0/g 0 | Q 0-1 | m 0/9 0 | Q 1-2 | m 0/g 0 | Q 3-4 |
12 | 3-4 | 5 | 4 | / | / | m 0/g 0 | Q 2 | / | / |
13 | 3-4 | 5 | 4 | m 2/g 1 | Q 0-1 | m 0/g 0 | Q 1-2 | m 0/g 0 | Q 3-4 |
14 | 5 | 5 | 4-5 | / | / | / | / | / | / |
15 | 5 | 5 | 4-5 | / | / | / | / | / | / |
16 | 3-4 | 5 | 3 | / | / | / | / | / | / |
17 | 3-4 | 4-5 | 3 | / | / | / | / | / | / |
18 | 3-4 | 4-5 | 3-4 | / | / | / | / | / | / |
19 | 3-4 | 4-5 | 3-4 | / | / | / | / | / | / |
20 | 3-4 | 4-5 | 3 | / | / | / | / | / | / |
zero | / | / | / | m 0/g 0 | Q 0 | m 0/g 0 | Q 0-1 | m 0/g 0 | Q 2-3 |
sample | to | to | to | to | |||||
m 1-2/g 1 | Q 1 | m 1/g 2 | Q 1 | ||||||
Table 2 shows, for comparison, the test results for the conventional pigments used in Comparative Examples 1 to 4.
In Comparative Examples 1 and 2, Iriodin® 9225 Rutile Pearlescent Blue, a titanium dioxide coated mica pigment, was employed. In Comparative Example 2, it was provided with an additional coating of compounds of chromium and manganese as described in EP 0 104 516, and in Comparative Example 1 it was provided with an additional coating of zirconium oxide hydrate, cerium oxide hydrate and an epoxy silane as described in EP 0 342 533.
In Comparative Examples 3 and 4, Iriodin® 9504 Red, an iron(III) oxide-coated mica pigment, was used. In Comparative Example 3 it was provided with an additional coating as described in EP 0 342 533, and in Comparative Example 4 it was provided with an additional coating as described in EP 0 104 516.
TABLE 2 |
Test results for the conventional pigments used in Comparative Examples 1 to 4 |
Condensation water test on water-thinnable | ||
Water immersion | surface-coating systems |
Comparative | Photo- | test | A | B | C |
Example | activity | 16 h/66° C. | 20 h/80° C. | Bubbles | Swelling | Bubbles | Swelling | Bubbles | Swelling |
1 | 3-4 | 3-4 | / | m 0/g 0 | Q 0 | m 0/g 0 | Q 3 | Q 4 | m 0/g 0 |
to | to | Q 3-4 | |||||||
m 3/g 1 | Q 1 | ||||||||
2 | 3 | 4-5 | / | m 0/g 0 | Q 0 | m 0/g 0 | Q 3-4 | m g/g 1 | Q 4-5 |
to | to | to | |||||||
m 4-5/g 1 | Q 1-2 | Q 4 | |||||||
3 | 5 | 4-5 | 4 | m 0/g 0 | Q 1 | m 0/g 0 | Q 3-4 | m 0/g 0 | Q 3 |
to | to | ||||||||
m 3/g 1 | Q 4 | ||||||||
4 | 5 | 4-5 | / | m 0/g 0 | Q 1-2 | m 0/g 0 | Q 3-4 | m 0/g 0 | Q 3-4 |
to | bis | to | |||||||
Q 3 | m 1/g 2 | Q 5 | |||||||
zero | / | / | / | m 0/g 0 | Q 0 | m 0/g 0 | Q 0-1 | m 0/g 0 | Q 2-3 |
sample | to | to | to | to | |||||
m 1-2/g 1 | Q 1 | m 1/g 2 | Q 1 | ||||||
The comparative examples show that the surface-coating systems containing the pigments according to the invention have significantly better swelling behavior than those containing conventional pigments (see water-borne surface-coating system B, Examples 10, 11, and 13).
The Examples below are intended to illustrate the invention without representing a limitation.
In the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees Celsius; and, unless otherwise indicated, all parts and percentages are by weight.
The entire disclosure of all applications, patents and publications, cited above and below, and of corresponding German Application No. P 43 21 005.8, filed Jun. 24, 1993, are hereby incorporated by reference.
100 g of Iriodin® 504 Red (iron(III) oxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous, stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 2.7 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes. 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 1.10 g of cerium(III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Hüls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silane is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid.
5.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
13.2 g of pure Manchem C (carboxyzirconium aluminate solution from Rhone-Poulenc Chemicals) are subsequently added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes and the zirconium aluminate coupling reagent are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, silanes of various functionality and zirconium aluminate are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
In addition, 5.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
13.2 g of pure Manchem C (carboxyzirconium aluminate solution from Rhone-Poulenc Chemicals) are subsequently added over the course of 10 minutes.
During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes and the zirconium aluminate coupling reagent are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, silanes of various functionality and zirconium aluminate are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.5 g of pure Z 6020 (N-2-aminoethyl-3-aminopropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid.
In addition, 3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
13.2 g of pure Manchem C (carboxyzirconium aluminate solution from Rhone-Poulenc Chemicals) are subsequently added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes and the zirconium aluminate coupling reagent are fully hydrolyzed and become reactive. The pH does not change. The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, silanes of various functionality and zirconium aluminate are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
13.2 g of pure Manchem C (carboxyzirconium aluminate solution from Rhone-Poulenc Chemicals) are subsequently added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silane and the zirconium aluminate coupling reagent are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, the silane and zirconium aluminate are coprecipitated completely. The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
13.2 g of pure Manchem C (carboxyzirconium aluminate solution from Rhone-Poulenc Chemicals) are subsequently added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the zirconium aluminate coupling reagent is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, and the zirconium aluminate are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
14.8 g of pure Manchem A (aminozirconium aluminate solution from Rhône Poulenc Chemicals) are subsequently added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the zirconium aluminate coupling reagent is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, and zirconium aluminate are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
14.8 g of pure Manchem M (methacrylzirconium aluminate solution from Rhone Poulenc Chemicals) are subsequently added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the zirconium aluminate coupling reagent is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates, and zirconium aluminate are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
3.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 90 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid.
In addition, 3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
3.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. In addition, 3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours. During this addition the silanes are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. In addition, 3.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring. The procedure of Example 1 is then followed as far as the addition of the coupling reagents.
3.5 g of pure Z 6020 (N-2-aminoethyl-3-aminopropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3 by means of 2.5% hydrochloric acid.
In addition, 3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
3.0 g of pure Z 6040 (3-glycidoxypropyltrimethoxysilane from Dow Corning Chemicals) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silanes are fully hydrolyzed and become reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silanes are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 504 Red (iron (III) oxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 5.4 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5 hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes. 2.70 g of sodium sulfate, 4.60 g of aluminum chloride hexahydrate and 1.10 of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silane is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 504 Red (iron (III) oxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 8.1 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes. 4.05 g of sodium sulfate, 6.90 g of aluminum chloride hexahydrate and 1.10 g of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
3.0 g of pure Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH is kept constant at 3.3 by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silane is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile (Pearlescent Blue titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 2.7 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes. 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 1.70 g of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silane is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely. The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineratized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile (Pearlescent Blue titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 2.7 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes. 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 2.25 g of cerium (III) chloride heptahydrate as solids are then added to the pigment suspension, during which the pH drops to 4.0.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 3.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
3.0 g of pure Dynasilan MEMO (3-methacryloxypropyltrimethoxysilane from Huls AG, Troisdorf) are then added over the course of 10 minutes. During this addition, the pH remains constant at 3.3. When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours, during which the silane is fully hydrolyzed and becomes reactive. The pH does not change.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 2.7 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5 hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
A solution of 1.35 g of sodium sulfate, 2.30 g aluminum chloride hexahydrate and 1.10 g of cerium (III) chloride heptahydrate, 2.62 g of zirconium (IV) oxide chloride octahydrate and 2 ml of 10% hydrochloric acid, dissolved in 100 ml of demineralized water, are subsequently added dropwise to the pigment suspension over the course of 15 minutes, during which the pH drops to 2.5.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 2.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
A solution of 3.0 g of Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) dissolved in 200 ml of demineralized water (= complete silane hydrolysis) is then added dropwise to the pigment suspension over the course of 15 minutes, during which the pH rises to 3.9.
When the addition is complete, the mixture is stirred at 75° C. for a further two hours. During this addition, the pH drops to 3.6.
The pH is subsequently adjusted to 8.0 very slowly over the course of 60 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 2.7 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture then adjusted 40° C. for a further 15 minutes. The pH is adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is-stirred at 40° C. for a further 15 minutes.
A solution of 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 1.10 g of cerium (III) chloride heptahydrate, 2.62 g of zirconium (IV) oxide chloride octahydrathydrochloric acid, dissolved in 100 ml of demineralized water, are subsequently added dropwise to the pigment suspension over the course of 15 minutes, during which the pH drops to 2.5.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 2.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
The pH is subsequently adjusted to 3.0 very slowly over the course of 20 minutes by means of 2.5% sodium hydroxide solution (= preneutralization).
A solution of 3.0 g of Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) dissolved in 200 ml of demineralized water (= complete silane hydrolysis) is then added dropwise to the pigment suspension over the course of 15 minutes, during which the pH rises to 4. 2.
When the addition is complete, the mixture is stirred at 75° C. for a further 2 hours. During this addition, the pH drops to 3.6.
The pH is subsequently adjusted to 8.0 very slowly over the course of 40 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
100 g of Iriodin® 225 Rutile Pearlescent Blue (titanium dioxide-coated mica pigment from E. Merck, Darmstadt) are suspended in 900 ml of demineralized water, and the suspension is heated to 40° C. with vigorous stirring.
The pH is adjusted to 9.0 by means of 2.5% sodium hydroxide solution. All the pH values indicated are determined with the aid of suitable pH indicator paper.
A solution of 2.7 ml of sodium water glass (370 g of SiO2 per liter) in 150 ml of demineralized water is subsequently added dropwise over the course of 30 minutes to the pigment suspension. During this addition, the pH is kept constant by means of 2.5% hydrochloric acid. When the addition is complete, the mixture is stirred at 40° C. for a further 15 minutes. The pH is then adjusted to 6.5 over the course of 10 minutes by means of 2.5% hydrochloric acid, and the mixture is stirred at 40° C. for a further 15 minutes.
A solution of 1.35 g of sodium sulfate, 2.30 g of aluminum chloride hexahydrate and 1.10 g of cerium (III) chloride heptahydrate, 2.62 g of zirconium (IV) oxide chloride octahydrate and 2 ml of 10% hydrochloric acid, dissolved in 100 ml of demineralized water, are subsequently added dropwise to the pigment suspension over the course of 15 minutes, during which the pH drops to 2.5.
The mixture is subsequently heated to 75° C. over the course of about 20 minutes and stirred at 75° C. for a further 75 minutes, during which the pH drops to 2.3. The metal hydroxides or metal oxide hydrates, at least in part, are precipitated during this time.
The pH is subsequently adjusted to 4.0 very slowly over the course of about 35 minutes by means of 2.5% sodium hydroxide solution (= preneutralization).
A solution of 3.0 g of Dynasilan AMMO (3-aminopropyltrimethoxysilane from Huls AG, Troisdorf) dissolved in 200 ml of demineralized water (= complete silane hydrolysis) is then added dropwise to the pigment suspension over the course of 15 minutes, during which the pH rises to 4.8.
When the addition is complete, the mixture is stirred at 75° C. for a further two hours. During this addition, the pH drops to 4.6.
The pH is subsequently adjusted to 8.0 very slowly over the course of 25 minutes by means of 2.5% sodium hydroxide solution. During this time, the metal hydroxides or metal oxide hydrates and the silane are coprecipitated completely.
The mixture is subsequently stirred at 75° C. for a further 1 hour to complete the reaction, during which the pH drops to about 7.0.
The product is subsequently filtered off with suction, washed with demineralized water until salt-free and dried at 140° C. for about 16 hours.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
Claims (24)
1. A pearlescent pigment comprising a metal oxide titanium dioxide-coated, platelet-shaped substrate and a top layer on the metal oxide titanium dioxide coating, wherein the top layer comprises silicon dioxide, at least one metal hydroxide or metal oxide hydrate and at least one organic coupling reagent and is chromium free.
2. A pearlescent pigment according to claim 1 , wherein the metal hydroxide or metal oxide hydrate is a hydroxide or oxyhydrate of cerium, aluminum or zirconium.
3. A pearlescent pigment according to claim 1 , wherein the coupling reagent is a zirconium aluminate, a metal acid ester or an organofunctional silane.
4. A process for the preparation of a pearlescent pigment comprising a metal oxide titanium dioxide-coated, platelet-shaped substrate and a top layer on the metal oxide titanium dioxide coating, comprising suspending the metal oxide titanium dioxide-coated substrate in water, depositing silicic acid by adding a water-soluble silicate at a pH from 6 to 9, then, after adding one or more water-soluble metal salts at a pH from 3 to 7 and heating to from 30° to 100° C., partly depositing the metal hydroxides or metal oxide hydrates, adding at least one coupling reagent and hydrolyzing at a pH from 3 to 4, and depositing the part of the metals remaining in solution as hydroxides or oxide hydrates together with the coupling reagent at a pH of from 4 to 8.5, and subsequently drying the pigment from 80° to 160° C.
5. The process according to claim 4 , wherein the metal hydroxide or metal oxide hydrate is a hydroxide or oxyhydrate of aluminum, cerium or zirconium.
6. The process according to claim 4 , wherein the coupling reagent is a zirconium aluminate, a metal acid ester or an organofunctional silane.
7. The process of claim 4 , wherein comprising, after adding one or more water-soluble metal salts, heating at from 40° to 75° C.
8. The process of claim 4 , wherein subsequent drying of the pigment is at 120° C. to 160° C.
9. The pigment of claim 1 , wherein the metal oxide titanium dioxide-coated, platelet-shaped substrate is mica, kaolin or glass coated with titanium dioxide, titanium dioxide mixed with iron (III) oxide, iron (III) oxide, chromium oxide, zirconium dioxide, tin dioxide or zinc oxide .
10. The pigment of claim 1 , wherein the top layer constitutes 4 to 20% by weight of the pigment.
11. The pigment of claim 1 , wherein the silicon dioxide in the top layer constitutes 1 to 3% by weight of the pigment, the at least one metal hydroxide or metal oxide hydrate in the top layer constitutes 1 to 5% by weight of the pigment and the coupling reagent in the top layer constitutes 2 to 12% by weight of the pigment.
12. The pigment of claim 1 , wherein the top layer is formed by depositing silicon dioxide on the substrate, subsequently depositing a portion of the metal hydroxide or metal oxide hydrate thereon and, then, depositing the remaining metal hydroxide or metal oxide hydrate and the coupling reagent, simultaneously, thereon.
13. The pigment of claim 2 , wherein a maximum of 50% by weight of the metal hydroxide or metal oxide hydrate are is deposited in the initial deposition without the coupling reagent.
14. The pigment of claim 1 , which consists of said coated substrate and top layer and wherein the top layer consists essentially of silicon dioxide, at least one metal hydroxide or metal oxide hydrate and at least one organic coupling reagent.
15. The pigment of claim 1 , wherein the top layer comprises silicon dioxide, at least one metal hydroxide or metal oxide hydrate of cerium, and at least one organofunctional silane.
16. A pearlescent pigment comprising a titanium dioxide-coated, platelet-shaped substrate and a top layer on the titanium dioxide coating, wherein the top layer consists of silicon dioxide, at least one metal hydroxide or metal oxide hydrate of cerium, aluminum or zirconium, and at least one organic coupling reagent which is zirconium aluminate, a metal acid ester or an organofunctional silane.
17. A pearlescent pigment comprising a titanium dioxide-coated, platelet-shaped substrate and a top layer on the titanium dioxide coating, wherein the top layer consists of silicon dioxide, a metal hydroxide or metal oxide hydrate of cerium, and at least one organofunctional silane.
18. A pearlescent pigment comprising a titanium dioxide-coated, platelet-shaped substrate and a top layer on the titanium dioxide coating, wherein the pearlescent pigment is chromium-free and wherein the top layer comprises silicon dioxide, at least one metal hydroxide or metal oxide hydrate and at least one organic coupling reagent.
19. A pearlescent pigment consisting of a titanium dioxide-coated, platelet-shaped substrate and a top layer on the titanium dioxide coating, wherein the top layer consists of silicon dioxide, at least one metal hydroxide or metal oxide hydrate and at least one organic coupling reagent.
20. The pigment of claim 1 wherein the top layer comprises sublayers.
21. The pigment of claim 15 wherein the top layer comprises sublayers.
22. The pigment of claim 18 wherein the top layer comprises sublayers.
23. The pigment of claim 19 wherein the top layer comprises sublayers.
24. A pearlescent pigment prepared by the process of claim 4 .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US12/574,739 USRE41858E1 (en) | 1993-06-24 | 2009-10-07 | Pearlescent pigment for water-borne surface-coating systems |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4321005 | 1993-06-24 | ||
DE4321005A DE4321005A1 (en) | 1993-06-24 | 1993-06-24 | Pearlescent pigment for water-based paint systems |
US08/265,721 US5472491A (en) | 1993-06-24 | 1994-06-24 | Pearlescent pigment for water-borne surface-coating systems |
US12/574,739 USRE41858E1 (en) | 1993-06-24 | 2009-10-07 | Pearlescent pigment for water-borne surface-coating systems |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US08/265,721 Reissue US5472491A (en) | 1993-06-24 | 1994-06-24 | Pearlescent pigment for water-borne surface-coating systems |
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USRE41858E1 true USRE41858E1 (en) | 2010-10-26 |
Family
ID=6491126
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US08/265,721 Ceased US5472491A (en) | 1993-06-24 | 1994-06-24 | Pearlescent pigment for water-borne surface-coating systems |
US12/574,739 Expired - Lifetime USRE41858E1 (en) | 1993-06-24 | 2009-10-07 | Pearlescent pigment for water-borne surface-coating systems |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US08/265,721 Ceased US5472491A (en) | 1993-06-24 | 1994-06-24 | Pearlescent pigment for water-borne surface-coating systems |
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US (2) | US5472491A (en) |
EP (1) | EP0632109B1 (en) |
JP (1) | JP3947573B2 (en) |
KR (1) | KR100325568B1 (en) |
CZ (1) | CZ154494A3 (en) |
DE (2) | DE4321005A1 (en) |
ES (1) | ES2122093T3 (en) |
FI (1) | FI110784B (en) |
TW (1) | TW340866B (en) |
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-
1993
- 1993-06-24 DE DE4321005A patent/DE4321005A1/en not_active Withdrawn
-
1994
- 1994-05-25 TW TW083104741A patent/TW340866B/en active
- 1994-06-22 EP EP94109608A patent/EP0632109B1/en not_active Expired - Lifetime
- 1994-06-22 ES ES94109608T patent/ES2122093T3/en not_active Expired - Lifetime
- 1994-06-22 CZ CZ941544A patent/CZ154494A3/en unknown
- 1994-06-22 DE DE59406761T patent/DE59406761D1/en not_active Expired - Lifetime
- 1994-06-23 FI FI943045A patent/FI110784B/en active
- 1994-06-23 KR KR1019940014386A patent/KR100325568B1/en not_active IP Right Cessation
- 1994-06-24 JP JP14341694A patent/JP3947573B2/en not_active Expired - Lifetime
- 1994-06-24 US US08/265,721 patent/US5472491A/en not_active Ceased
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2009
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015013763A1 (en) * | 2013-07-29 | 2015-02-05 | Sg Ventures Pty Limited | Coated particles and method of coating particles |
AU2014295912B2 (en) * | 2013-07-29 | 2017-12-07 | CoLabs Int’l., Corp. | Coated particles and method of coating particles |
EP3211043A1 (en) | 2016-02-23 | 2017-08-30 | Merck Patent GmbH | Effect pigments based on al2o3-flakes |
EP3211043B1 (en) * | 2016-02-23 | 2020-05-13 | Merck Patent GmbH | Effect pigments based on al2o3-flakes |
US11453789B2 (en) | 2016-02-23 | 2022-09-27 | Merck Patent Gmbh | Effect pigments |
US11459469B2 (en) | 2016-02-23 | 2022-10-04 | Merck Patent Gmbh | Effect pigments |
US11479681B2 (en) | 2016-02-23 | 2022-10-25 | Merck Patent Gmbh | Effect pigments |
Also Published As
Publication number | Publication date |
---|---|
EP0632109B1 (en) | 1998-08-26 |
CZ154494A3 (en) | 1995-01-18 |
FI110784B (en) | 2003-03-31 |
FI943045A (en) | 1994-12-25 |
KR950000816A (en) | 1995-01-03 |
KR100325568B1 (en) | 2002-10-31 |
DE59406761D1 (en) | 1998-10-01 |
FI943045A0 (en) | 1994-06-23 |
TW340866B (en) | 1998-09-21 |
JP3947573B2 (en) | 2007-07-25 |
EP0632109A1 (en) | 1995-01-04 |
DE4321005A1 (en) | 1995-01-05 |
ES2122093T3 (en) | 1998-12-16 |
JPH0718199A (en) | 1995-01-20 |
US5472491A (en) | 1995-12-05 |
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