WO1997015382A1 - Dispersants for inorganic materials in aqueous systems - Google Patents
Dispersants for inorganic materials in aqueous systems Download PDFInfo
- Publication number
- WO1997015382A1 WO1997015382A1 PCT/US1996/016271 US9616271W WO9715382A1 WO 1997015382 A1 WO1997015382 A1 WO 1997015382A1 US 9616271 W US9616271 W US 9616271W WO 9715382 A1 WO9715382 A1 WO 9715382A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- maleic anhydride
- alpha
- anhydride copolymer
- hydrolyzed
- group
- Prior art date
Links
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 63
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 11
- 239000011147 inorganic material Substances 0.000 title claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 239000004711 α-olefin Substances 0.000 claims abstract description 41
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 239000012736 aqueous medium Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 17
- 229910001413 alkali metal ion Chemical class 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000004816 latex Substances 0.000 claims description 10
- 229920000126 latex Polymers 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 230000000475 sunscreen effect Effects 0.000 claims description 5
- 239000000516 sunscreening agent Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001023 inorganic pigment Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000008278 cosmetic cream Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 description 25
- 239000002245 particle Substances 0.000 description 18
- 239000002537 cosmetic Substances 0.000 description 13
- -1 decyl ester Chemical class 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000005233 alkylalcohol group Chemical group 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000037072 sun protection Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005041 Mylar™ Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- QYYMDNHUJFIDDQ-UHFFFAOYSA-N 5-chloro-2-methyl-1,2-thiazol-3-one;2-methyl-1,2-thiazol-3-one Chemical compound CN1SC=CC1=O.CN1SC(Cl)=CC1=O QYYMDNHUJFIDDQ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920004896 Triton X-405 Polymers 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 0 *c1ccc(*=C)cc1* Chemical compound *c1ccc(*=C)cc1* 0.000 description 1
- OVYMWJFNQQOJBU-UHFFFAOYSA-N 1-octanoyloxypropan-2-yl octanoate Chemical compound CCCCCCCC(=O)OCC(C)OC(=O)CCCCCCC OVYMWJFNQQOJBU-UHFFFAOYSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 0.000 description 1
- GDHWAMVEOAWHIM-UHFFFAOYSA-N 2-hydroxyoctacosyl 12-hydroxyoctadecanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)COC(=O)CCCCCCCCCCC(O)CCCCCC GDHWAMVEOAWHIM-UHFFFAOYSA-N 0.000 description 1
- 241001340526 Chrysoclista linneella Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 241000364021 Tulsa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- UPOYFZYFGWBUKL-UHFFFAOYSA-N amiphenazole Chemical compound S1C(N)=NC(N)=C1C1=CC=CC=C1 UPOYFZYFGWBUKL-UHFFFAOYSA-N 0.000 description 1
- 229950001798 amiphenazole Drugs 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229940081733 cetearyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008341 cosmetic lotion Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- STORWMDPIHOSMF-UHFFFAOYSA-N decanoic acid;octanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCC(O)=O.CCCCCCCCCC(O)=O STORWMDPIHOSMF-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 1
- GKKMCECQQIKAHA-UHFFFAOYSA-N hexadecyl dihydrogen phosphate;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCOP(O)(O)=O GKKMCECQQIKAHA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002966 varnish 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
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 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
- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/34—Higher-molecular-weight carboxylic acid esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/044—Suspensions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/28—Zirconium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Definitions
- the present invention relates to an improved process for preparation of a dispersion of inorganic pigments and other inorganic materials in aqueous systems comprising incorporation therein of particular dispersants.
- the dispersants comprise alpha-olefin maleic anhydride polymers, hydrolyzed partial esters and esters thereof, or esterified hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers.
- the present invention also relates to improved aqueous metal oxide compositions, latex surface coating compositions and cosmetic compositions and dried coatings of such compositions.
- Dispersants are used to prevent settling of solid particles in liquid media.
- the solid particles or pigment must be well dispersed in the liquid medium to provide optimum properties in films or coatings and to improve their performance.
- An effective dispersant prevents settling and occlusion of the solids and enables a uniform distribution of the solid material in the medium. Further the dispersion must remain stable during commercial processing and be effective in sufficiently low economical concentrations.
- U. S. Patent 3,322,713 describes a dispersing agent used to disperse organic materials in aqueous or organic media comprising a salt of an alkyl ester of an olefin-maleic anhydride copolymer having as cation, an alkali metal, an ammonium or a substituted ammonium, having a weight average molecular weight of up to about 10,000, having the alkyl ester portion derived from an alkyl alcohol having 3-18 carbon atoms.
- An aqueous dispersion of an organic pigment is prepared by dissolving the organic dispersing agent in an aqueous medium, and adding the organic pigment to the aqueous medium while agitating.
- U. S. Patent 5,001,004 discloses stain resistant compositions for use on textiles which are comprised of hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers.
- Ethylenically unsaturated aromatic compounds include styrene among others.
- the number average molecular weight for styrene/ maleic anhydride polymer is 500-4000.
- After preparing a styrene-maleic anhydride it is hydrolyzed using sodium, potassium and/ or lithium hydroxide, or, when using special measures, ammonium hydroxide in order to prepare polymers suitable for use as stain resists.
- hydrolysis should not be carried out in the presence of an alcohol, because then the ethylenically unsaturated aromatic/maleic anhydride polymer can react with the alcohol to form a half -ester, which is deleterious to the stain resist performance of the hydrolyzed polymer.
- Dispersants having improved properties over those currently available are needed for use in a variety of applications, in particular for dispersing inorganic materials in aqueous systems.
- a dispersant which can improve film and paint properties in a disperse system relative to available dispersants is therefore desirable.
- the present invention comprises an improved process for the preparation of a dispersion of inorganic materials in an aqueous medium, wherein the improvement comprises incorporating into the aqueous medium a dispersant selected from the group consisting of 1) a hydrolyzed ester of an ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin maleic anhydride copolymer, which can be used to disperse inorganic materials in aqueous systems.
- the present invention further comprises an improved aqueous metal oxide composition, an improved latex surface coating composition, and an improved cosmetic composition, wherein the improvement in each comprises incorporating therein a dispersant as described above.
- the invention further comprises dried coatings of such compositions.
- the present invention provides an improved process for the preparation of a dispersion of inorganic materials in an aqueous medium.
- the dispersants useful herein when incorporated into dispersions of an inorganic material in aqueous medium, improve the properties and/ or performance of the dispersion.
- the dispersants useful in the process of the present invention comprise 1) a hydrolyzed ester of an ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) an alpha-olefin/maleic anhydride copolymer or 3) a hydrolyzed partial ester of an alpha-olefin/ maleic anhydride copolymer.
- Preferred are octene- maleic anhydride partial decyl ester and styrene-maleic anhydride partial decyl ester.
- the hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer has polymeric units of formula I:
- is an alkyl of 1 to 18 carbon atoms
- X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions
- Y is O, S, NR!, or NH
- R5 is H, CH3 or phenyl
- R is H or CH3
- R3 is H or CH3O
- R4 is H, CH3 or CH3C(0)0; and R3 and R4 can be taken together to be
- n 1 to 50.
- the hydrolyzed alpha-olefin/maleic anhydride copolymer has polymeric units of formula II: ⁇ [ ⁇ (CH 2 -CHR) m — CH— CH— ] n — II
- R is an alpha-olefinic group having 4 to 16 carbon atoms
- X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions
- m is 1 to 10
- n is 1 to 50.
- the hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer has polymeric units of formula III: -[-(CH 2 -CHR) m — CH— CH-] n — III
- R is an alpha-olefinic group having 4 to 16 carbon atoms
- Rl is an alkyl of 1 to 18 carbon atoms
- X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRi, or NH; m is 1 to 10; and n is 1 to 50.
- dispersants are useful in aqueous formulations with a range of metal oxide particles such as oxides of tin, titanium, chromium, iron, vanadium, cobalt, copper, nickel, zinc, silver, molybdenum, manganese, tungsten, antimony doped tin, zirconium, aluminum, yttrium, europium, silica or mixtures thereof.
- metal oxide particles such as oxides of tin, titanium, chromium, iron, vanadium, cobalt, copper, nickel, zinc, silver, molybdenum, manganese, tungsten, antimony doped tin, zirconium, aluminum, yttrium, europium, silica or mixtures thereof.
- tin oxide-based electroconductive powders such as ZELEC ECP-3010- XC and titanium dioxide powders, such as TI-PURE and UFT-520AL, all available from E. I. du Pont de Nemours and Company, Wilmington, Delaware.
- Such formulations include opaque paints, clear coatings and varnishes, electroconductive paints, static-dissipative coatings, conductive coatings, oil-in-water and water-in-oil emulsions, and emulsions for cosmetic purposes.
- Preferred formulations contain a polyester resin and an agent for crosslinking the resin.
- the coatings formed from the dispersions become more transparent.
- Emulsions which are made from ultrafine titanium dioxide and these dispersants are transparent when rubbed onto the skin, with no whitish residue, and also give good protection from ultraviolet (UV) radiation. Therefore the process of the present invention is useful in the preparation of improved dispersions, in particular, improved paint, cosmetic, and electroconductive compositions.
- Preparation of the dispersants used in the process and compositions of the present invention is achieved by first preparing a maleic anhydride copolymer.
- Ethylenically unsaturated aromatic monomers which may be used to prepare the aromatic/maleic anhydride copolymer dispersant can be represented by formula:
- R5 is H, CH3 or phenyl;
- R ⁇ is H or CH3;
- R3 is H or CH3O-;
- R4 is H, CH3, or CH3C(0)0; and
- R3 and R4 can be taken together to form -0-CH 2 -0-.
- a copolymer of the ethylenically unsaturated aromatic monomer and maleic anhydride can be prepared with a molar ratio of aromatic to maleic anhydride typically about 1:1 as dictated by chemical reactivity.
- the copolymer can have number average molecular weights in the range between about 500 and 5000, preferably between about 800 and 2000, and an acid number of about 150 to 500.
- the copolymers are readily soluble in water at neutral to alkaline pH. Increasing dilution is required at a pH below 6.
- the copolymers are also soluble in lower alcohols, such as methanol, and are somewhat soluble in acetic acid. Procedures for producing styrene-maleic anhydride copolymers are well known to skilled artisans.
- a styrene-maleic anhydride copolymer resin which is commercially available and suitable for use in this invention is SMA-1000 available from Atochem North America Inc., 3 Parkway, Philadelphia, Pennsylvania 19102.
- the ester portion of this dispersant is derived from alkyl alcohols having an aliphatic moiety of 1-18 carbon atoms.
- Typical examples of the alcohols that can be used are propyl alcohol, butyl alcohol, decyl alcohol, and octadecyl alcohol.
- the amount of alcohol added relative to the amount of the ethylenically unsaturated aromatic/maleic anhydride copolymer is from 10 mole percent to 50 mole percent, perferably from 20 mole percent to 40 mole percent, most preferably about 30 mole percent.
- Mole percent is used to refer to the total moles of acid groups available (not the total moles of compound available). These conditions are such to achieve partial esterification.
- Suitable hydrolyzing agents for preparing the dispersants from the esterified copolymer include alkali metal hydroxides, especially sodium hydroxide, and ammonium or substituted ammonium hydroxides.
- the amount of hydrolyzing agent present can be from about 10:1 to about 1:1 as a molar ratio, typically about 1:1.
- alkyl alcohol having an aliphatic moiety of 1-18 carbon atoms is added to the heated copolymer solution over a period of time of from about 5 to about 200 minutes. This mixture is then maintained at a temperature of from about 60°C to about 100°C for a time of from about 3 to about 24 hours, preferably at about 100°C for about 6 hours, to esterify the copolymer.
- the temperature of the mixture containing the esterified copolymer is adjusted to about 60°C.
- To the esterified copolymer is then added a sufficient amount of a hydrolyzing agent to fully hydrolyze the esterified copolymer.
- the mixture is stirred for from about 10 to about 60 minutes.
- After the hydrolysis step the mixture is cooled to ambient temperature and the product is analyzed for percent solids.
- the pH is adjusted to 8-9 and the percent solids is adjusted to a desired range suitable for the end use intended.
- This preparation process is represented by the following reaction sequence wherein R is an ethylenically unsaturated aromatic group, R x is Ci-C ⁇ g alkyl, m and n represent the number of repeating units in the copolymer and X is a positively charged ion selected from the group consisting of an alkali metal ion such as sodium ion, potassium ion, ammonium ion, or substituted ammonium ion.
- R is an ethylenically unsaturated aromatic group
- R x is Ci-C ⁇ g alkyl
- m and n represent the number of repeating units in the copolymer
- X is a positively charged ion selected from the group consisting of an alkali metal ion such as sodium ion, potassium ion, ammonium ion, or substituted ammonium ion.
- a second dispersant useful in the process and compositions of the present invention is a hydrolyzed alpha-olefin/maleic anhydride copolymer, or a hydrolyzed partial or full ester thereof.
- Suitable olefins which may be used to prepare the olefin/ maleic anhydride copolymer include alpha-olefins having 4 to 18 carbon atoms.
- a copolymer of the olefin and maleic anhydride can be prepared using a molar ratio of olefin to maleic anhydride of from about 0.25:1 to about 4.0:1. Preferably the amount of maleic anhydride is maximized consistent with effective polymerization.
- Alpha-olefin/maleic anhydride copolymers useful in the present invention are commercially available from Petrolite Corporation, 6910 E. 14th Street, Tulsa, Oklahoma 74112. The alpha-olefin/maleic anhydride copolymers are then hydrolyzed. Suitable hydrolyzing agents for preparing dispersants from the copolymer include alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, and ammonium or substituted arnmonium hydroxides.
- the amount of hydrolyzing agent as a molar ratio to alpha-olefin/maleic anhydride copolymer used is from about 10:1 to about 1:1, typically about 1:1.
- the hydrolyzed alpha-olefin/maleic anhydride copolymer is useful as a dispersant for inorganic materials in aqueous systems.
- a third dispersant useful in the process and compositions of the present invention is a hydrolyzed partially esterified alpha-olefin/maleic anhydride copolymer.
- the ester portion of these dispersants is derived from alkyl alcohols having an aliphatic moiety of 1-18 carbon atoms.
- Typical examples of the alcohols which can be used are propyl alcohol, butyl alcohol, decyl alcohol, and octadecyl alcohol.
- the ratio of alcohol relative to the amount of maleic anhydride in the copolymer is from about 0.01:1 to about 1:1, preferably from about 0.3:1 to about 0.8:1.
- the partially esterified alpha-olefin/maleic anhydride polymers are suitable for use in the present invention after being hydrolyzed.
- the alkyl esters of an alpha-olefin-maleic anhydride copolymer employed in the practice of this invention may be prepared as described above for the first dispersant.
- the present invention further comprises improved aqueous metal oxide coating compositions of an oxide of a metal selected from the group consisting of tin, titanium, chromium, iron, antimony, vanadium, cobalt, copper, nickel, zinc, silver, molybdenum, manganese, tungsten, antimony doped tin, zirconium, aluminum, yttrium, europium, or a mixture thereof, dispersed in an aqueous medium such as water wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed
- At least one of the three types of dispersants prepared as described above is dissolved, usually under agitation, in a portion of an aqueous medium, such as water.
- the inorganic solids are then added under agitation, and are milled for example with 0.8 to 1 millimeter zirconium silicate beads for 24 hours.
- the solids are then adjusted to the desired concentration by addition of the remainder of the aqueous medium.
- the metal oxide particles may provide another functionality other than filler. For example; if electroconductive tin oxide particles are used, a transparent conductive coating may be made. If titanium dioxide particles of less than 0.1 micron diameter are used, a coating which is transparent to visible light but absorbs ultraviolet light may be made. To obtain transparency, the metal oxide particles are preferably less than 0.1 micron in diameter.
- titanium dioxide compositions include titanium dioxide compositions.
- the improved titanium dioxide compositions have incorporated therein a dispersant selected from the group consisting of 1) a hydrolyzed partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolyer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer.
- a dispersant selected from the group consisting of 1) a hydrolyzed partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolyer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer.
- These titanium dioxide compositions are able to absorb and scatter ultraviolet light and therefore are useful as ingredients in sunscreen formulations and
- Suitable dispersant-to-pigment ratios are less than about 0.3/1; preferably less than 0.05/1 in compositions having a percentage of ultrafine titanium solids of about 70% or less.
- the degree of dispersion may be evaluated by obtaining the particle size in the particles in the dispersion, using either standard transmission electron microscopy or low angle laser light scattering.
- titanium dioxide compositions to absorb and scatter ultraviolet light makes them useful as ingredients in many other compositions such as food packaging materials, wood coating, coatings on vinyl and other architectural materials, glass coatings, and automotive clearcoats.
- the dispersants used herein have a wide range of compatibility with acrylic, urethane, polyester and other resins. Preparation of such coatings are well known and are described in Myers, R.R. and Long J.S. (Eds) "Treatise on Coatings", Vol. 4, Part I; formulations, Marcel Dekker, New York, New York (1975.)
- the present invention further comprises an improved aqueous latex surface coating composition (paint composition) comprising a water soluble inorganic pigment dispersed in an aqueous latex of a film-forming polymer wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin.maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alphaolef in/ maleic anhydride copolymer.
- a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin.maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alphaole
- the improved latex coating compositions i.e., paints
- the improved paints of the present invention are prepared by conventional techniques known in the art. Such formulation techniques are described, for example, in G.P. A. Turner, "Introduction to Paint Chemistry and Principles of Paint Technology” 2nd Ed., Chapman and Hall Ltd., New York, New York (1980).
- the present invention also comprises a dry coating composition comprising the above described metal oxide compositions, latex surface coating compositions, and titanium dioxide compositions in dried form after application to a substrate.
- Example 1 Into a 1000 ml round bottom flask fitted with a mechanical stirrer, condenser, and nitrogen inlet and having a feedback controlled heating mantle, was placed 250 grams of water and then 125 grams of SMA 1000, a 1:1 copolymer of styrene and maleic anhydride having a number average molecular weight of 1600, available from Atochem North America Inc., 3 Parkway, Philadelphia, Pennsylvania 19102. The contents of the flask were heated to 80°C at which time, 24 grams of decyl alcohol was added over a 2 hour period. The mixture was heated overnight and cooled to 60°C. At that time, 60 grams of 28% ammonium hydroxide in 300 ml of water was added. After addition, the contents of the flask were stirred for 30 minutes and analyzed for percent solids. Solids were determined by washing the solution, heating in a vacuum oven to remove solvent and reweighing. Active ingredient was 17.5%.
- Example 2 A latex paint was made of the following formula:
- Rhoplex SG-10M 495.00 (224.53) 56.02 (212.0)
- Foamaster VL is available from Henkel Corporation, Ambler, Pennsylvania 19002.
- Kathon LX, Rhoplex SG-10M, Triton X-405 and Acrysol 1020 are available from Rohm & Haas Company, Philadelphia, Pennsylvania.
- Texanol is available from Eastman Chemical Company, Rochester, New York 14650.
- Ti0 2 is available from E. I. du Pont de Nemours and Company, Wilmington, Delaware.
- the Ti0 2 was first wetted with water and dispersant to a 70-80 weight to weight ratio. Then the first 11 materials listed above were mixed and ground for 30 minutes. A "pre-mix” containing Acrysol 1020 and water was then prepared and added to the ground mixture for a "let-down” step. This mixture was mixed an additional 10-15 minutes to provide the paint.
- a comparative paint was prepared in the same manner as described above with the exception that instead of a dispersant of this invention, 5.40 lb (2.4 kg) or 0.55 gal (0.21 cc) of a commercial dispersant, (50%), and 12.0 lbs (5.44 kg) or 1.44 gal (0.54 cc) of water in place of 2.6 lb (1.18 kg) or 0.31 gal (0.12 cc) of water, was used.
- the hiding power of each paint was measured by the following procedure which is related to ASTM D2805.
- a drawdown of the paint to be tested was made on preweighed Morest Chart using a bird film applicator blade at 0.90- 0.95 contrast ratio at 72°F, (22°C) 50% relative humidity.
- the treated chart was weighed 20 seconds after the drawdown had been completed. Quadruplicate drawdowns were made. The average weight of the four drawdowns was used in the calculation.
- A is the Kubelka-Munk chart value
- A area of paint film in square inches. 1550 is the square inches per square meter
- d is the paint density in pounds per gallon.
- Wf is the weight of wet paint film in grams.
- C is the concentration of Ti0 in paint in pounds per gallon.
- the 60 degree gloss of each paint was measured according to ASTM D523, hereby incorporated by reference. Using an automatic drawdown machine at 0.002 inches, a film of each paint was applied to separate black PVC panels.
- Gloss LSV + [ ⁇ (SMR - LMR) / (HMR - LMR) ⁇ x (HSV - LSV) ].
- LSV is the assigned low standard value.
- HSV is the assigned high standard value.
- LMR is the low standard meter reading.
- HMR is the high standard meter reading.
- SMR is the sample meter reading
- Example 3 A dispersion of ultrafine titanium dioxide was prepared as follows.
- a master dispersion was prepared by mixing 30 grams of ultrafine Ti0 2 with 15 grams of the dispersant prepared in Example 1, 28% by weight in water, and 346 grams of water. This mixture was milled in a Union Process 01 research attritor using 0.8 mm zirconium silicate beads at 500 rpm for 24 hours to provide a dispersion of finely divided particles of ultrafine powder. 5 grams of this master dispersion was mixed with 18.2 grams of Carboset 514H, aqueous acrylic resin, available from B. F.
- the dispersion (resin & metal oxide mixture) was spread onto a transparent support (e.g. mylar, transparencies).
- a Hunter ColorQUEST with D65 Illuminant, and 2 degree observer angle was used to provide and collect the light. The light was shone through a 1" diameter piece of sample. Both the amount of transmitted diffuse light and total transmitted light was measured.
- the % Haze 100* (diffuse transmitted/ total transmitted). Samples of less than 10% Haze are considered somewhat transparent; samples of less than 3% Haze are considered transparent.
- the low haze values obtained in thiese examples were an indication of good dispersion and low white cast, and were desirable for cosmetic applications.
- the comparative examples used were commercially available dispersants as follows: A) 1 propanol ester of styrene/ maleic anhydride copolymer,
- Comparative examples A, B and C were ammonia neutralized and are representative of a hydrolyzed, partially esterified ethylenically unsaturated aromatic maleic anhydride copolymer dispersants.
- Comparative example D is representative of a hydrolyzed alpha-olefin maleic anhydride copolymer.
- Comparative example E is available from E. I. du Pont de Nemours and Company, Wilmington, Delaware.
- Example 6 decylester of styrene maleic anhydride copolymer.
- Examples 4 and 5 were sodium neutralized and are repesentaive of a hydrolyzed alpha-olefin/maleic anhydride copolymer dispersant.
- Example 6 was ammonia neutralized and is representaitve of a hydrolyzed partially esterified ethylenically unsaturated aromatic maleic anhydride copolymer dispersant.
- Examples 7-8 Compositions were prepared in water similarly to those above in Example 4-6, but with different dispersion to pigment ratios and pigment to binder (resin) ratios. The compositions were tested for haze and transparency as in Examples 4-6.
- the dispersants employed were as follows: Comprative F) diisobutylene/ maleic anhydride copolymer, Example 7) 1 -octene maleic anhydride copolymer Example 8) 1 -octene maleic anhydride copolymer Resulting data is listed in Table II:
- a composition was prepared in water similarly to those in Examples 4-
- the metal oxide employed was an electroconductive powder, antimony doped tin.
- the dispersant used was a 1-octene xylene maleic anhydride terpolymer. The compositions were tested for haze, and transparency as previously described and for surface resistivity using a Monroe
- the method used was in accordance with literature supplied with the equipment.
- the sample was placed on top of the nonconductive ground plate.
- the meter was set to a voltage of one (1) volt.
- the probe was then placed on the sample and a stable resistance value determined.
- a #8 wirewound rod was used to make a drawdown of this dispersion.
- Example 10 A composition was prepared as in Example 9 above using a 1 -octene maleic anhydride copolymer dispersant and tested for surface resistivity, haze and transparency as previously described. COMPONENT GRAMS
- This millbase was drawndown with a #8 wirewound rod.
- Surface resistivity was 22 kiloohms/ square. Haze was 2.2%; total transmitted light was 78.5%.
- Example 11 A cosmetic lotion was prepared according to the following formula:
- Cetearyl alcohol TA1618 (Proctor & Gamble) 0.5
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Abstract
In an improved process for the preparation of a dispersion of inorganic materials in an aqueous medium, the improvement comprising incorporating into the aqueous medium a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer, and the resulting compositions are disclosed.
Description
TITLE DISPERSANTS FOR INORGANIC MATERIALS IN AQUEOUS SYSTEMS
FIELD OF THE INVENTION The present invention relates to an improved process for preparation of a dispersion of inorganic pigments and other inorganic materials in aqueous systems comprising incorporation therein of particular dispersants. The dispersants comprise alpha-olefin maleic anhydride polymers, hydrolyzed partial esters and esters thereof, or esterified hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers. The present invention also relates to improved aqueous metal oxide compositions, latex surface coating compositions and cosmetic compositions and dried coatings of such compositions.
BACKGROUND OF THE INVENTION Dispersants are used to prevent settling of solid particles in liquid media. For disperse systems such as paints, cosmetics and other formulations, the solid particles or pigment must be well dispersed in the liquid medium to provide optimum properties in films or coatings and to improve their performance. An effective dispersant prevents settling and occlusion of the solids and enables a uniform distribution of the solid material in the medium. Further the dispersion must remain stable during commercial processing and be effective in sufficiently low economical concentrations.
U. S. Patent 3,322,713 describes a dispersing agent used to disperse organic materials in aqueous or organic media comprising a salt of an alkyl ester of an olefin-maleic anhydride copolymer having as cation, an alkali metal, an ammonium or a substituted ammonium, having a weight average molecular weight of up to about 10,000, having the alkyl ester portion derived from an alkyl alcohol having 3-18 carbon atoms. An aqueous dispersion of an organic pigment is prepared by dissolving the organic dispersing agent in an aqueous medium, and adding the organic pigment to the aqueous medium while agitating.
U. S. Patent 5,001,004 discloses stain resistant compositions for use on textiles which are comprised of hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers. Ethylenically unsaturated aromatic compounds include styrene among others. The number average molecular weight
for styrene/ maleic anhydride polymer is 500-4000. After preparing a styrene-maleic anhydride, it is hydrolyzed using sodium, potassium and/ or lithium hydroxide, or, when using special measures, ammonium hydroxide in order to prepare polymers suitable for use as stain resists. It is directed that hydrolysis should not be carried out in the presence of an alcohol, because then the ethylenically unsaturated aromatic/maleic anhydride polymer can react with the alcohol to form a half -ester, which is deleterious to the stain resist performance of the hydrolyzed polymer.
Dispersants having improved properties over those currently available are needed for use in a variety of applications, in particular for dispersing inorganic materials in aqueous systems. A dispersant which can improve film and paint properties in a disperse system relative to available dispersants is therefore desirable.
SUMMARY OF THE INVENTION The present invention comprises an improved process for the preparation of a dispersion of inorganic materials in an aqueous medium, wherein the improvement comprises incorporating into the aqueous medium a dispersant selected from the group consisting of 1) a hydrolyzed ester of an ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin maleic anhydride copolymer, which can be used to disperse inorganic materials in aqueous systems. The present invention further comprises an improved aqueous metal oxide composition, an improved latex surface coating composition, and an improved cosmetic composition, wherein the improvement in each comprises incorporating therein a dispersant as described above. The invention further comprises dried coatings of such compositions.
DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improved process for the preparation of a dispersion of inorganic materials in an aqueous medium. The dispersants useful herein, when incorporated into dispersions of an inorganic material in aqueous medium, improve the properties and/ or performance of the dispersion.
The dispersants useful in the process of the present invention comprise 1) a hydrolyzed ester of an ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) an alpha-olefin/maleic anhydride copolymer or 3) a hydrolyzed partial ester of an alpha-olefin/ maleic anhydride copolymer. Preferred are octene-
maleic anhydride partial decyl ester and styrene-maleic anhydride partial decyl ester.
The hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer has polymeric units of formula I:
-[-(CH2-CHR)m-CH-CH--]n-- I
I I c=o c=o
I I
YRl OX wherein
R| is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions;
Y is O, S, NR!, or NH;
R is
wherein R2 is R5-CH=C(R6)-, or CH2=CH=CH2;
R5 is H, CH3 or phenyl;
R is H or CH3;
R3 is H or CH3O; and
R4 is H, CH3 or CH3C(0)0; and R3 and R4 can be taken together to be
-O-CH2-O-; m is 1 to 10; and n is 1 to 50.
The hydrolyzed alpha-olefin/maleic anhydride copolymer has polymeric units of formula II: ~[~(CH2-CHR)m — CH— CH— ]n— II
c=o c=o
I I ox ox wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; m is 1 to 10; and n is 1 to 50.
The hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer has polymeric units of formula III: -[-(CH2-CHR)m — CH— CH-]n — III
I I c=o c=o
I I YRl OX wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms; Rl is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRi, or NH; m is 1 to 10; and n is 1 to 50.
These dispersants are useful in aqueous formulations with a range of metal oxide particles such as oxides of tin, titanium, chromium, iron, vanadium, cobalt, copper, nickel, zinc, silver, molybdenum, manganese, tungsten, antimony doped tin, zirconium, aluminum, yttrium, europium, silica or mixtures thereof. Included are tin oxide-based electroconductive powders, such as ZELEC ECP-3010- XC and titanium dioxide powders, such as TI-PURE and UFT-520AL, all available from E. I. du Pont de Nemours and Company, Wilmington, Delaware. Such formulations include opaque paints, clear coatings and varnishes, electroconductive paints, static-dissipative coatings, conductive coatings, oil-in-water and water-in-oil emulsions, and emulsions for cosmetic purposes. Preferred formulations contain a polyester resin and an agent for crosslinking the resin.
When used to disperse pigmentary-sized particles, that is , particles of about 0.2 to 20 microns, preferably 0.2 to 0.6 microns, properties such as hiding power and gloss are improved. When used to disperse ultrafine particles, that is, particles of less than 0.2 microns, preferably less than 0.1 microns diameter, the coatings formed from the dispersions become more transparent. Emulsions which are made from ultrafine titanium dioxide and these dispersants are transparent when rubbed onto the skin, with no whitish residue, and also give good protection from ultraviolet (UV) radiation. Therefore the process of the present invention is
useful in the preparation of improved dispersions, in particular, improved paint, cosmetic, and electroconductive compositions.
Preparation of the dispersants used in the process and compositions of the present invention is achieved by first preparing a maleic anhydride copolymer. Ethylenically unsaturated aromatic monomers which may be used to prepare the aromatic/maleic anhydride copolymer dispersant can be represented by formula:
wherein R2 is Rs-CH=C (R6)- or CH2=CH-CH2=; R5 is H, CH3 or phenyl; Rβ is H or CH3; R3 is H or CH3O-; and R4 is H, CH3, or CH3C(0)0; and R3 and R4 can be taken together to form -0-CH2-0-.
A copolymer of the ethylenically unsaturated aromatic monomer and maleic anhydride can be prepared with a molar ratio of aromatic to maleic anhydride typically about 1:1 as dictated by chemical reactivity. The copolymer can have number average molecular weights in the range between about 500 and 5000, preferably between about 800 and 2000, and an acid number of about 150 to 500. The copolymers are readily soluble in water at neutral to alkaline pH. Increasing dilution is required at a pH below 6. The copolymers are also soluble in lower alcohols, such as methanol, and are somewhat soluble in acetic acid. Procedures for producing styrene-maleic anhydride copolymers are well known to skilled artisans. A styrene-maleic anhydride copolymer resin which is commercially available and suitable for use in this invention is SMA-1000 available from Atochem North America Inc., 3 Parkway, Philadelphia, Pennsylvania 19102.
The ester portion of this dispersant is derived from alkyl alcohols having an aliphatic moiety of 1-18 carbon atoms. Typical examples of the alcohols that can be used are propyl alcohol, butyl alcohol, decyl alcohol, and octadecyl alcohol. The amount of alcohol added relative to the amount of the ethylenically unsaturated aromatic/maleic anhydride copolymer is from 10 mole percent to 50 mole percent, perferably from 20 mole percent to 40 mole percent, most preferably about 30 mole percent. Mole percent is used to refer to the total moles of acid groups available (not the total moles of compound available). These conditions are such to achieve partial esterification. It is preferred that less than half of the acid groups are esterified.
Suitable hydrolyzing agents for preparing the dispersants from the esterified copolymer include alkali metal hydroxides, especially sodium hydroxide, and ammonium or substituted ammonium hydroxides. The amount of hydrolyzing agent present can be from about 10:1 to about 1:1 as a molar ratio, typically about 1:1.
To prepare the hydrolyzed esters of ethylenically unsaturated aromatic/maleic anhydride copolymers used in this invention, first an ethylenically unsaturated aromatic/maleic anhydride copolymer is stirred into water. These copolymers are soluble in water if base is added. The copolymer solution is heated to a temperature of from 60 to 100°C.
An alkyl alcohol having an aliphatic moiety of 1-18 carbon atoms is added to the heated copolymer solution over a period of time of from about 5 to about 200 minutes. This mixture is then maintained at a temperature of from about 60°C to about 100°C for a time of from about 3 to about 24 hours, preferably at about 100°C for about 6 hours, to esterify the copolymer.
The temperature of the mixture containing the esterified copolymer is adjusted to about 60°C. To the esterified copolymer is then added a sufficient amount of a hydrolyzing agent to fully hydrolyze the esterified copolymer. The mixture is stirred for from about 10 to about 60 minutes. After the hydrolysis step, the mixture is cooled to ambient temperature and the product is analyzed for percent solids. The pH is adjusted to 8-9 and the percent solids is adjusted to a desired range suitable for the end use intended.
This preparation process is represented by the following reaction sequence wherein R is an ethylenically unsaturated aromatic group, Rx is Ci-C^g alkyl, m and n represent the number of repeating units in the copolymer and X is a positively charged ion selected from the group consisting of an alkali metal ion such as sodium ion, potassium ion, ammonium ion, or substituted ammonium ion.
A second dispersant useful in the process and compositions of the present invention is a hydrolyzed alpha-olefin/maleic anhydride copolymer, or a hydrolyzed partial or full ester thereof. Suitable olefins which may be used to prepare the olefin/ maleic anhydride copolymer include alpha-olefins having 4 to 18 carbon atoms. A copolymer of the olefin and maleic anhydride can be prepared using a molar ratio of olefin to maleic anhydride of from about 0.25:1 to about 4.0:1. Preferably the amount of maleic anhydride is maximized consistent with effective polymerization. Procedures for producing olefin/ maleic anhydride copolymers are well known in the art. Alpha-olefin/maleic anhydride copolymers useful in the present invention are commercially available from Petrolite Corporation, 6910 E. 14th Street, Tulsa, Oklahoma 74112. The alpha-olefin/maleic anhydride copolymers are then hydrolyzed. Suitable hydrolyzing agents for preparing dispersants from the copolymer include alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, and ammonium or substituted arnmonium hydroxides. The amount of hydrolyzing agent as a molar ratio to alpha-olefin/maleic anhydride copolymer used is from about 10:1 to about 1:1, typically about 1:1. The hydrolyzed alpha-olefin/maleic anhydride copolymer is useful as a dispersant for inorganic materials in aqueous systems.
A third dispersant useful in the process and compositions of the present invention is a hydrolyzed partially esterified alpha-olefin/maleic anhydride copolymer. The ester portion of these dispersants is derived from alkyl alcohols
having an aliphatic moiety of 1-18 carbon atoms. Typical examples of the alcohols which can be used are propyl alcohol, butyl alcohol, decyl alcohol, and octadecyl alcohol. The ratio of alcohol relative to the amount of maleic anhydride in the copolymer is from about 0.01:1 to about 1:1, preferably from about 0.3:1 to about 0.8:1. The partially esterified alpha-olefin/maleic anhydride polymers are suitable for use in the present invention after being hydrolyzed.
The alkyl esters of an alpha-olefin-maleic anhydride copolymer employed in the practice of this invention may be prepared as described above for the first dispersant. The present invention further comprises improved aqueous metal oxide coating compositions of an oxide of a metal selected from the group consisting of tin, titanium, chromium, iron, antimony, vanadium, cobalt, copper, nickel, zinc, silver, molybdenum, manganese, tungsten, antimony doped tin, zirconium, aluminum, yttrium, europium, or a mixture thereof, dispersed in an aqueous medium such as water wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer. To make the improved coatings of the present invention, at least one of the three types of dispersants prepared as described above is dissolved, usually under agitation, in a portion of an aqueous medium, such as water. The inorganic solids are then added under agitation, and are milled for example with 0.8 to 1 millimeter zirconium silicate beads for 24 hours. The solids are then adjusted to the desired concentration by addition of the remainder of the aqueous medium. The metal oxide particles may provide another functionality other than filler. For example; if electroconductive tin oxide particles are used, a transparent conductive coating may be made. If titanium dioxide particles of less than 0.1 micron diameter are used, a coating which is transparent to visible light but absorbs ultraviolet light may be made. To obtain transparency, the metal oxide particles are preferably less than 0.1 micron in diameter.
Included within the improved aqueous metal oxide coating compositions of the present invention are titanium dioxide compositions. The improved titanium dioxide compositions have incorporated therein a dispersant selected from the group consisting of 1) a hydrolyzed partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolyer, and 3) a hydrolyzed partial ester of an
alpha-olefin/maleic anhydride copolymer. These titanium dioxide compositions are able to absorb and scatter ultraviolet light and therefore are useful as ingredients in sunscreen formulations and cosmetics formulations, such as creams or lotions. Such sunscreen and cosmetic formulations are also included within the present invention. Processes for preparation of such sunscreens and cosmetics are well known in the art. For example, for preparation of sunscreens and cosmetics see Dahms, Cosmetics and Toiletries, 107, pp. 133-143, (Oct. 1992), or Woodruff, J., "Formulating Sun Care Products with Micronized Oxides," Cosmetics and Toiletries Manufacture Worldwide, 1994 (Aston) pp. 179-185. Data on improved sun protection factors for titanium dioxide compositions of the present invention are provided in the examples hereinafter. The compositions are transparent to visible light while providing excellent ultraviolet screening properties. Suitable dispersant-to-pigment ratios (D/P) are less than about 0.3/1; preferably less than 0.05/1 in compositions having a percentage of ultrafine titanium solids of about 70% or less. The degree of dispersion may be evaluated by obtaining the particle size in the particles in the dispersion, using either standard transmission electron microscopy or low angle laser light scattering.
The ability of the titanium dioxide compositions to absorb and scatter ultraviolet light makes them useful as ingredients in many other compositions such as food packaging materials, wood coating, coatings on vinyl and other architectural materials, glass coatings, and automotive clearcoats. The dispersants used herein have a wide range of compatibility with acrylic, urethane, polyester and other resins. Preparation of such coatings are well known and are described in Myers, R.R. and Long J.S. (Eds) "Treatise on Coatings", Vol. 4, Part I; formulations, Marcel Dekker, New York, New York (1975.)
The present invention further comprises an improved aqueous latex surface coating composition (paint composition) comprising a water soluble inorganic pigment dispersed in an aqueous latex of a film-forming polymer wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin.maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alphaolef in/ maleic anhydride copolymer. The improved latex coating compositions, i.e., paints, have improved gloss and hiding power when compared to conventional paints due to the improved dispersion as demonstrated in the examples hereinafter. The improved paints of the present invention are prepared by conventional techniques known in the art. Such formulation techniques are described, for example, in G.P. A. Turner,
"Introduction to Paint Chemistry and Principles of Paint Technology" 2nd Ed., Chapman and Hall Ltd., New York, New York (1980).
The present invention also comprises a dry coating composition comprising the above described metal oxide compositions, latex surface coating compositions, and titanium dioxide compositions in dried form after application to a substrate.
EXAMPLES Example 1 Into a 1000 ml round bottom flask fitted with a mechanical stirrer, condenser, and nitrogen inlet and having a feedback controlled heating mantle, was placed 250 grams of water and then 125 grams of SMA 1000, a 1:1 copolymer of styrene and maleic anhydride having a number average molecular weight of 1600, available from Atochem North America Inc., 3 Parkway, Philadelphia, Pennsylvania 19102. The contents of the flask were heated to 80°C at which time, 24 grams of decyl alcohol was added over a 2 hour period. The mixture was heated overnight and cooled to 60°C. At that time, 60 grams of 28% ammonium hydroxide in 300 ml of water was added. After addition, the contents of the flask were stirred for 30 minutes and analyzed for percent solids. Solids were determined by washing the solution, heating in a vacuum oven to remove solvent and reweighing. Active ingredient was 17.5%.
Example 2 A latex paint was made of the following formula:
RAW MATERIAL LBS. (KG, GAL. Liters
Water 2.6 (1.18) 0.31 (1.2)
Propylene Glycol 65.00 (29.48) 7.51 (28.4)
Dispersant of Example 1 15.00 (2.40) 1.56 (5.91)
Foamaster VL 1.00 (0.45) 0.13 (0.49)
Kathon LX (1.5%) 1.70 (0.77) 0.20 (0.76)
Ti02 Ti-Pure®R-706 268.00 (121.56) 8.04 (30.4)
Water 88.00 (39.92) 10.56 (39.97)
Rhoplex SG-10M 495.00 (224.53) 56.02 (212.0)
Texanol 18.50 (8.39) 2.33 (8.82)
Triton X-405 2.50 (1.13) 0.27 (1.0)
Foamaster VL 1.00 (0.45) 0.13 (0.49)
Acrysol 1020 39.50 (17.92) 4.57 (17.3)
Water 68.66 (31.14) 8.24 (31.2)
Foamaster VL is available from Henkel Corporation, Ambler, Pennsylvania 19002. Kathon LX, Rhoplex SG-10M, Triton X-405 and Acrysol 1020 are available from Rohm & Haas Company, Philadelphia, Pennsylvania. Texanol is available from Eastman Chemical Company, Rochester, New York 14650. Ti02 is available from E. I. du Pont de Nemours and Company, Wilmington, Delaware.
The Ti02 was first wetted with water and dispersant to a 70-80 weight to weight ratio. Then the first 11 materials listed above were mixed and ground for 30 minutes. A "pre-mix" containing Acrysol 1020 and water was then prepared and added to the ground mixture for a "let-down" step. This mixture was mixed an additional 10-15 minutes to provide the paint.
A comparative paint was prepared in the same manner as described above with the exception that instead of a dispersant of this invention, 5.40 lb (2.4 kg) or 0.55 gal (0.21 cc) of a commercial dispersant, (50%), and 12.0 lbs (5.44 kg) or 1.44 gal (0.54 cc) of water in place of 2.6 lb (1.18 kg) or 0.31 gal (0.12 cc) of water, was used.
The hiding power of each paint was measured by the following procedure which is related to ASTM D2805. A drawdown of the paint to be tested was made on preweighed Morest Chart using a bird film applicator blade at 0.90- 0.95 contrast ratio at 72°F, (22°C) 50% relative humidity. The treated chart was weighed 20 seconds after the drawdown had been completed. Quadruplicate drawdowns were made. The average weight of the four drawdowns was used in the calculation.
Reflectance readings were made of the drawdowns on a Gardner Automatic Multipurpose Reflectometer available from Byk Gardner Company, Silver Springs, Maryland 20910 using green filter. One reading was taken on each of two "white" and "black" sections of each of the four charts. Contrast ratio was calculated by dividing the average reflectance over the black area by the average over the white. Scattering power (SX value) is read from the appropriate Kubelka- Munk Opacity Chart chosen by substrate reflectance using values of contrast ratio and reflectance over black.
The scattering coefficient (S) in units of square meters per gram of τjfj2 was calculated by the following: S = [ (SX) (A) (d) ] / [ (Wf) (C) (1550) ] SX . A is the Kubelka-Munk chart value A = area of paint film in square inches. 1550 is the square inches per square meter, d is the paint density in pounds per gallon. Wf is the weight of wet paint film in grams. C is the concentration of Ti0 in paint in pounds per gallon.
The 60 degree gloss of each paint was measured according to ASTM D523, hereby incorporated by reference. Using an automatic drawdown machine at 0.002 inches, a film of each paint was applied to separate black PVC panels. Each treated panel was placed in an environmental chamber at 108°F (87°C) at 60% relative humidity for 3 hours and 3 minutes. The 60 degree Gloss was read using a Gardner Haze-Gloss meter, catalog number 4606, available from Byk Gardner Company, Silver Springs, Maryland 20910. At least two readings were taken from each panel. The average reading was used as the gloss meter reading of that sample. Gloss is corrected by the following formula: Gloss = LSV + [ { (SMR - LMR) / (HMR - LMR) } x (HSV - LSV) ]. LSV is the assigned low standard value. HSV is the assigned high standard value. LMR is the low standard meter reading. HMR is the high standard meter reading. SMR is the sample meter reading
In comparing the hiding power and gloss values of the two paints, it was found that the hiding power was increased by 13% and the 60 degree gloss was improved by 5 degrees in the paint containing the dispersant of this invention relative to the paint containing the commercial dispersant.
Example 3 A dispersion of ultrafine titanium dioxide was prepared as follows. A master dispersion was prepared by mixing 30 grams of ultrafine Ti02 with 15 grams of the dispersant prepared in Example 1, 28% by weight in water, and 346 grams of water. This mixture was milled in a Union Process 01 research attritor using 0.8 mm zirconium silicate beads at 500 rpm for 24 hours to provide a dispersion of finely divided particles of ultrafine powder. 5 grams of this master dispersion was mixed with 18.2 grams of Carboset 514H, aqueous acrylic resin, available from B. F. Goodrich, 9911 Brecksville Rd, Brecksville, Ohio 44141, to provide a dispersion containing 5% Ti02 based on the dry weight of the Ti02 and the resin. A drawdown of this dispersion was made onto a polypropylene sheet using a #8 rod. The sun protection factor (SPF) was determined by the procedure and was found to be 3.9. A second dispersion of ultrafine Ti02 was prepared in the same manner as described above with the exception that a commercial dispersant, was used instead of a dispersant of this invention. The SPF of this second dispersion was 1.6.
Determination of sun protection factors was performed by the method of Duffey and Robson, J. Soc. Cosmet. Chem., 1989, 40, pp. 127-133, hereby incorporated by refrence. An Optometrics SPF-290 Analyzer (available from Optometrics USA Inc., Auer, Massachusetts.) and described by Sellers and
Carpenter in Cosmetics and Toiletries, 1992, 107, pp. 119-122, hereby incorporated by reference, was used. As noted above polypropylene sheet was used as the substrate to coat with the dispersions instead of the surgical tape used in the above references. Examples 4 -6
All of the compositions listed in Table I below were made as follows: 7.7% UFT-520AL - Ultrafine Titanium Dioxide available from E. I. du Pont de Nemours and Company, Wilmington, Delaware; 1.1% dispersant; and 91.2% distilled water, were milled in a Union Process 01 attritor mill for 24 hours. 450 grams of millbase were loaded, with 850 grams of 0.8 to 1mm zirconium silicate beads. After milling the beads were filtered out, and 1 gram of the resultant millbase was added to 4.4 grams of aqueous polyester resin (Eastman AQ38, 30% solids, available from Eastman Chemical Company, Rochester, New York). A drawdown (dry resin/ metal oxide mixture on a support) of this dispersion onto Mylar (grade GA-10; 5 mils thick) available from E. I. du Pont de Nemours and Company, Wilmington, Delaware, was made with a #8 wirewound rod (nominal 20.5 microns dry film thickness). The film thus formed was about 5.5% Ti02 and 94.5% resin. Haze and transparency measurements were then taken on a Hunter ColorQUEST available from Hunter Associates Laboratory, Inc., 11491 -T Sunset Hills Rd., Reston, Virginia 22090, D65 Illuminant, 2 degree observer angle using the following method.
The dispersion (resin & metal oxide mixture) was spread onto a transparent support (e.g. mylar, transparencies). A Hunter ColorQUEST with D65 Illuminant, and 2 degree observer angle was used to provide and collect the light. The light was shone through a 1" diameter piece of sample. Both the amount of transmitted diffuse light and total transmitted light was measured. The % Haze = 100* (diffuse transmitted/ total transmitted). Samples of less than 10% Haze are considered somewhat transparent; samples of less than 3% Haze are considered transparent. The low haze values obtained in thiese examples were an indication of good dispersion and low white cast, and were desirable for cosmetic applications. Another drawdown was made by mixing 1 gram of the millbase with 18.2 grams Carboset 514H aqueous acrylic resin (BF Goodrich Specialty Chemicals, 9911 Brecksville Rd., Cleveland, Ohio. A #8 wirewound rod was used to make drawdowns onto polypropylene film. UV/ visible absorption measurements were taken, and the SPF (sun protection factor) was also measured using the method given in Example 3. The SPF values in the table below showed that the ultrafine
titanium dioxide particles still absorbed and scattered UV rays, thus protecting the substrate from the UV, while remaining transparent.
The comparative examples used were commercially available dispersants as follows: A) 1 propanol ester of styrene/ maleic anhydride copolymer,
B) 2-butoxyethylester of styrene/ maleic anhydride copolymer,
C) Mixed cyclohexanol isopropyl ester of styrene/ maleic anhydride copolymer,
D) diisobutylene/ maleic anhydride copolymer,
E) phosphate ester of perfluoroalkyl ethylalcohol. Comparative examples A, B and C were ammonia neutralized and are representative of a hydrolyzed, partially esterified ethylenically unsaturated aromatic maleic anhydride copolymer dispersants. Comparative example D is representative of a hydrolyzed alpha-olefin maleic anhydride copolymer. Comparative example E is available from E. I. du Pont de Nemours and Company, Wilmington, Delaware.
The dispersants used in examples 4-6 were as follows:
4) 1-octene xylene maleic anhydride terpolymer,
5) 1 -octene maleic anhydride copolymer,
6) decylester of styrene maleic anhydride copolymer. Examples 4 and 5 were sodium neutralized and are repesentaive of a hydrolyzed alpha-olefin/maleic anhydride copolymer dispersant. Example 6 was ammonia neutralized and is representaitve of a hydrolyzed partially esterified ethylenically unsaturated aromatic maleic anhydride copolymer dispersant.
TABLE I
%TRANS
COMPARATIVE EXAMPLES HAZE PARENCY SPF
A 11.5 89.4 4.1
B 9.2 89.1 4.9
C 9.6 89.2 5.2
D 15.5 90.1 1.6
E 15.5 90.5 2.5
EXAMPLES
4 3.8 87.8 5.5
5 3.1 89.3 5.1
6 5.2 88.6 4.4
The data in Table I show that the compositions of the present invention were much more effective than the commercially available comparative examples, since the haze values are considerably lower. The mylar sheet used gave a haze value of about 1.0. Example 4, gave a median particle size of 0.077 and the largest particle size was 0.36 (unsonicated); but Example A, gave median particle size of 0.115 and the largest particle size was 1.1 microns (unsonicated).
Examples 7-8 Compositions were prepared in water similarly to those above in Example 4-6, but with different dispersion to pigment ratios and pigment to binder (resin) ratios. The compositions were tested for haze and transparency as in Examples 4-6. The dispersants employed were as follows: Comprative F) diisobutylene/ maleic anhydride copolymer, Example 7) 1 -octene maleic anhydride copolymer Example 8) 1 -octene maleic anhydride copolymer Resulting data is listed in Table II:
TABLE II
EXAMPLE %UFT-a %DISPERSANT D/P HAZE %TRANSC
Comparative F 7.7 0.2 0.025 28.5 91.2
7 7.7 0.16 0.021 8.5 88.9
8 40 2.1 0.053 6.3 88.4 a Percent ultrafine titanium dioxide b Dispersant to pigment ratio c % Transparency Example 9
A composition was prepared in water similarly to those in Examples 4-
6 above but no ultrafine Ti0 was employed. The metal oxide employed was an electroconductive powder, antimony doped tin. The dispersant used was a 1-octene xylene maleic anhydride terpolymer. The compositions were tested for haze, and transparency as previously described and for surface resistivity using a Monroe
Model 278 Precision Resistance/ Current Meter with a Monroe Model 96117-1
Surface/ Volume Resistivity Set Probe available from Monroe Electronics, Inc. 100
Housel Ave., Lyndonville, NY 14098. The method used was in accordance with literature supplied with the equipment. The sample was placed on top of the nonconductive ground plate. The meter was set to a voltage of one (1) volt. The probe was then placed on the sample and a stable resistance value determined.
COMPONENT GRAMS
H20 197
Dispersant, (28%) 7.1 Polyester resin AQ55S(21.4%)* 156
Antimony doped tin, ZELEC ECP-3010-XC** 100
TOTAL: 460
Pigment to binder (resin) ratio = 3/1; Dispersant to pigment ratio = 0.02/1.
* From Eastman Chemical Co. Rochester, New York ** From E. I. du Pont de Nemours and Company, Wilmington, Delaware
A #8 wirewound rod was used to make a drawdown of this dispersion.
Surface resistivity was 16 kiloohms/ square. Haze was 4.1%; total transmitted light was 78.4%.
Example 10 A composition was prepared as in Example 9 above using a 1 -octene maleic anhydride copolymer dispersant and tested for surface resistivity, haze and transparency as previously described.
COMPONENT GRAMS
H20 195
Dispersant (21.3%) 9.4
Polyester Resin AQ55S(21.4%)* 156
Antimony doped tin, ZELEC ECP-3010-XC** 100
TOTAL: 460
Pigment to binder (resin) ratio = 3/1; Dispersant to pigment ratio = 0.02/1.
* From Eastman Chemical Co., Rochester, New York
** From E. I. du Pont de Nemours and Company, Wilmington, Delaware
This millbase was drawndown with a #8 wirewound rod. Surface resistivity was 22 kiloohms/ square. Haze was 2.2%; total transmitted light was 78.5%.
Example 11 A cosmetic lotion was prepared according to the following formula:
CTFA NAME BRAND USED COMPANY AMOUNT (GRAMS,
Propylene glycol dicaprylate Liponate PC (LIPO) 5
Dimethicone (lOOcs) (Dow Corning) 3
Cetyl phosphate and
DEA cetyl phosphate Amphisol K (Givaudan-Roure) 2
Caprylic/ capric triglyceride Liponate GC (LIPO) 7
Hydroxyoctacosanyl hydroxystearate Elfacos C26 (AKZO) 2
Cetearyl alcohol TA1618 (Proctor & Gamble) 0.5
Glyceryl stearate Cerasynt SD (ISP Van Dyk) 5
Mineral Oil (Baker) 3
Total Oil Phase 27.5
Magnesium aluminum silicate Veegum (RT Vanderbilt) 2
Propylene glycol (Baker) 5
Dispersion of 7.7% Ti02, 02% UFT520AL (E. I. duPont de Nemours 65.2
1-octene maleic anhydride- and Co.) copolymer dispersant, water
Total Water Phase 72.2
TOTAL 99.7
* UFT = ultrafine titanium dioxide
A SPF of 7 was obtained using the dispersion of Example 4. The lotion thus formed has been stable for 12 months.
Claims
1. In an improved process for the preparation of a dispersion of inorganic materials in an aqueous medium, the improvement comprising incorporating into the aqueous medium a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer.
2. The process of Claim 1 wherein
1) the hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer has polymeric units of formula I: ~[~(CH2-CHR)m— CH — CH — ]n- I
I I c=o c=o
I I YRα OX wherein
Rl is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRi. or NH;
R is
R3 is H or CH3O; and
R4 is H, CH3 or CH3C(0)0; and
R3 and R4 can be taken together to be
-0-CH2-0-; m is 1 to 10; and n is 1 to 50;
2) the hydrolyzed alpha-olefin/maleic anhydride copolymer has polymeric units of formula II: ~[-(CH2-CHR)m— -CH— CH— ]n— II
I I c=o c=o
I I ox ox wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; m is 1 to 10; amd n is 1 to 50; and 3) the hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer has polymeric units of formula III: ~[-(CH2-CHR)m — CH— CH~]n — III
c=o c=o
YRl OX wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms; Rx is an alkyl of 1 to 18 carbon atoms; X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, orNH; m is 1 to 10; and n is 1 to 50.
3. The process of Claim 1 wherein the dispersant has a number average molecular weight of from about 500 to about 5000, and wherein the alpha- olefin/maleic anhydride copolymer has a ratio of units derived from alcohol to units derived from maleic anhydride of from about 0.1:1 to about 1:1.
4. An improved aqueous metal oxide composition comprising an oxide of a metal selected from the group consisting of tin, titanium, chromium, iron, antimony, vanadium, cobalt, copper, nickel, zinc, silver, molybdenum, manganese, tungsten, antimony doped tin, zirconium, aluminum, yttrium, europium, silica and mixtures thereof dispersed in an aqueous medium wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer.
5. The metal oxide composition of Claim 5 wherein
1) the hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer has polymeric units of formula I:
-[-(CH2-CHR)m--CH-CH-]n— I
I I c=o c=o I I
YRl OX wherein
Rl is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, or NH; R is
R6 is H or CH3; R3 is H or CH3O; and R4 is H, CH3 or CH3C(0)0; and R3 and R4 can be taken together to be -0-CH2-0-; m is 1 to 10; and n is 1 to 50; 2) the hydrolyzed alpha-olefin/maleic anhydride copolymer has polymeric units of formula II:
~[~(CH2-CHR)m— -CH— CH— ]n— II
I I c=o c=o
I I ox ox wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms; X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; m is 1 to 10; and n is 1 to 50; and 3) the hydrolyzed partial ester of an alpha- olefin/maleic anhydride copolymer has polymeric units of formula III: -[-(CH2-CHR)m— CH— CH— ]n— III
I I c=o c=o I I
YRl OX wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms; Rl is an alkyl of 1 to 18 carbon atoms; X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, or NH; m is 1 to 10; and n is 1 to 50.
6. The composition of Claim 5 formulated as a clear coating or a static- dissipative coating.
7. The composition of Claim 5 further comprising a polyester resin and an agent for crosslinking said resin.
8. An improved aqueous latex surface coating composition comprising a water soluble inorganic pigment dispersed in an aqueous latex of a film-forming polymer wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer.
9. The latex surface coating composition of Claim 9 wherein:
1) the hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer has polymeric units of formula I:
~[~(CH2-CHR)m— -CH— CH-]n-
I I c=o c=o
I I
YRl OX wherein
Rl is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, or NH; R is
R is H or CH3;
R3 is H or CH3O; and
R is H, CH3 or CH3C(0)0; and
R3 and R4 can be taken together to be -0-CH2-0-; m is 1 to 10; and n is 1 to 50; 2) the hydrolyzed alpha-olefin/maleic anhydride copolymer has polymeric units of formula II: ~[~(CH2-CHR)m — CH— CH— ]n— II
I I c=o c=o
I I ox ox wherein R is an alpha-olefinic group having 4 to 16 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; m is 1 to 10; and n is 1 to 50;
3) the hydrolyzed partial ester of an alpha- olefin/maleic anhydride copolymer has polymeric units of formula III:
__[__(CH2-CHR)m--CH-CH-ln» III
c=o c=o
YRl OX wherein
R is an alpha-olefinic group having 4 to 16 carbon atoms; Rl is an alkyl of 3 to 18 carbon atoms; X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, or NH; m is 1 to 10; and n is 1 to 50.
10. An improved titanium dioxide composition wherein the improvement comprises incorporating therein a dispersant selected from the group consisting of 1) a hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer, 2) a hydrolyzed alpha-olefin/maleic anhydride copolymer, and 3) a hydrolyzed partial ester of an alpha-olefin/maleic anhydride copolymer.
11. The improved titanium dioxide composition of Claim 10 wherein 1) the hydrolyzed, partially esterified ethylenically unsaturated aromatic/maleic anhydride copolymer has polymeric units of formula I: -[_(CH2-CHR)m— CH-CH-]n~ I
I I c=o c=o I I
YRl OX wherein
Rl is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, orNH; R is
wherein R2 is Rs-CH=C(R6)-, or CH2=CH=CH ; R5 is H, CH3 or phenyl; R is H or CH3; R3 is H or CH3O; and R4 is H, CH3 or CH3C(0)0; and R3 and R4 can be taken together to be -0-CH2-0-; m is 1 to 10; and n is 1 to 50;
2) the hydrolyzed alpha-olefin/maleic anhydride copolymer has polymeric units of formula II: ~[~(CH2-CHR)m— -CH— CH— ]n— II I I c=o c=o
I I ox ox wherein R is an alpha-olefinic group having 4 to 16 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; m is 1 to 10; and n is 1 to 50; 3) the hydrolyzed partial ester of an alpha- olefin/maleic anhydride copolymer has polymeric units of formula III: ~[~(CH2-CHR)m— -CH— CH— ]n— III I I c=o c=o
I I
YRl OX wherein R is an alpha-olefinic group having 4 to 16 carbon atoms;
Rl is an alkyl of 1 to 18 carbon atoms;
X is selected from the group consisting of ammonium, substituted ammonium, and alkali metal ions; Y is O, S, NRι, or NH; m is 1 to 10; and n is 1 to 50.
12. The titanium dioxide composition of Claim 11 formulated as a cosmetic cream, lotion, sunscreen or sunblock.
13. A dry coating comprising the composition of Claim 5, 9 or 11.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU74381/96A AU7438196A (en) | 1995-10-27 | 1996-10-11 | Dispersants for inorganic materials in aqueous systems |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US54898895A | 1995-10-27 | 1995-10-27 | |
US08/548,988 | 1995-10-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997015382A1 true WO1997015382A1 (en) | 1997-05-01 |
Family
ID=24191201
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/016271 WO1997015382A1 (en) | 1995-10-27 | 1996-10-11 | Dispersants for inorganic materials in aqueous systems |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU7438196A (en) |
WO (1) | WO1997015382A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0889102A2 (en) * | 1997-06-30 | 1999-01-07 | Elf Atochem North America, Inc. | Pigment dispersion for the preparation of aqueous inks |
WO2000020519A2 (en) * | 1998-10-07 | 2000-04-13 | Bayer Aktiengesellschaft | Preparations containing fine-particulate inorganic oxides |
WO2003103620A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag | Highly concentrated aqueous dispersions containing hydrophobic microfine metal oxide particles and a dispersant |
WO2003103619A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag | Highly concentrated aqueous dispersions containing hydrophilic microfine metal oxide particles and a dispersant |
WO2006067457A1 (en) * | 2004-12-23 | 2006-06-29 | Eastman Kodak Company | Dispersant for reducing viscosity of particulate solids |
WO2007079213A2 (en) * | 2005-12-30 | 2007-07-12 | E. I. Du Pont De Nemours And Company | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
EP1905417A2 (en) * | 2004-08-27 | 2008-04-02 | MERCK PATENT GmbH | Utilisation of statistical copolymers |
US7427316B2 (en) | 2005-12-30 | 2008-09-23 | E.I. Du Pont De Nemours And Company | Tropolone complexes as wood preservatives |
US7462227B2 (en) | 2005-12-30 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Ibuprofen complexes as wood preservatives |
US20090176070A1 (en) * | 2005-12-22 | 2009-07-09 | Hiroshi Goto | Pigment Dispersion, Recording Ink, Ink Cartridge, Ink-Jet Recording Method and Ink-Jet Recording Apparatus |
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GB758986A (en) * | 1953-08-11 | 1956-10-10 | Rohm & Haas | Improvements in or relating to aqueous dispersions of pigments |
EP0541477A1 (en) * | 1991-11-04 | 1993-05-12 | Rheox International, Inc. | Antisettling agents for aqueous coating compositions |
JPH0834953A (en) * | 1994-07-22 | 1996-02-06 | Sk Kaken Co Ltd | Water-based titanium paste having high pigment content |
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1996
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- 1996-10-11 WO PCT/US1996/016271 patent/WO1997015382A1/en active Application Filing
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GB758986A (en) * | 1953-08-11 | 1956-10-10 | Rohm & Haas | Improvements in or relating to aqueous dispersions of pigments |
EP0541477A1 (en) * | 1991-11-04 | 1993-05-12 | Rheox International, Inc. | Antisettling agents for aqueous coating compositions |
JPH0834953A (en) * | 1994-07-22 | 1996-02-06 | Sk Kaken Co Ltd | Water-based titanium paste having high pigment content |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0889102A2 (en) * | 1997-06-30 | 1999-01-07 | Elf Atochem North America, Inc. | Pigment dispersion for the preparation of aqueous inks |
EP0889102A3 (en) * | 1997-06-30 | 1999-01-20 | Elf Atochem North America, Inc. | Pigment dispersion for the preparation of aqueous inks |
WO2000020519A2 (en) * | 1998-10-07 | 2000-04-13 | Bayer Aktiengesellschaft | Preparations containing fine-particulate inorganic oxides |
WO2000020519A3 (en) * | 1998-10-07 | 2001-11-29 | Bayer Ag | Preparations containing fine-particulate inorganic oxides |
WO2003103620A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag | Highly concentrated aqueous dispersions containing hydrophobic microfine metal oxide particles and a dispersant |
WO2003103619A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag | Highly concentrated aqueous dispersions containing hydrophilic microfine metal oxide particles and a dispersant |
EP1905417A2 (en) * | 2004-08-27 | 2008-04-02 | MERCK PATENT GmbH | Utilisation of statistical copolymers |
EP1905417A3 (en) * | 2004-08-27 | 2008-06-11 | MERCK PATENT GmbH | Utilisation of statistical copolymers |
WO2006067457A1 (en) * | 2004-12-23 | 2006-06-29 | Eastman Kodak Company | Dispersant for reducing viscosity of particulate solids |
US8153716B2 (en) | 2004-12-23 | 2012-04-10 | Eastman Kodak Company | Dispersant for reducing viscosity of particulate solids |
US8383700B2 (en) | 2005-12-22 | 2013-02-26 | Ricoh Company, Ltd. | Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus |
US20090176070A1 (en) * | 2005-12-22 | 2009-07-09 | Hiroshi Goto | Pigment Dispersion, Recording Ink, Ink Cartridge, Ink-Jet Recording Method and Ink-Jet Recording Apparatus |
US8242201B2 (en) * | 2005-12-22 | 2012-08-14 | Ricoh Company, Ltd. | Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus |
WO2007079213A3 (en) * | 2005-12-30 | 2007-11-22 | Du Pont | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
US7540906B2 (en) | 2005-12-30 | 2009-06-02 | E.I. Du Pont De Nemours & Company | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
US7462227B2 (en) | 2005-12-30 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Ibuprofen complexes as wood preservatives |
US7427316B2 (en) | 2005-12-30 | 2008-09-23 | E.I. Du Pont De Nemours And Company | Tropolone complexes as wood preservatives |
WO2007079213A2 (en) * | 2005-12-30 | 2007-07-12 | E. I. Du Pont De Nemours And Company | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
Also Published As
Publication number | Publication date |
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AU7438196A (en) | 1997-05-15 |
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