CN101283053A - 颜料制剂 - Google Patents
颜料制剂 Download PDFInfo
- Publication number
- CN101283053A CN101283053A CNA2006800366609A CN200680036660A CN101283053A CN 101283053 A CN101283053 A CN 101283053A CN A2006800366609 A CNA2006800366609 A CN A2006800366609A CN 200680036660 A CN200680036660 A CN 200680036660A CN 101283053 A CN101283053 A CN 101283053A
- Authority
- CN
- China
- Prior art keywords
- pigment
- preparation
- dispersant resin
- weight
- polyalkylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 262
- 238000002360 preparation method Methods 0.000 title claims abstract description 90
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000002270 dispersing agent Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000008199 coating composition Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000009736 wetting Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000000975 dye Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- -1 vinyl compound Chemical class 0.000 description 21
- 239000000178 monomer Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000012463 white pigment Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000004922 lacquer Substances 0.000 description 8
- 239000001054 red pigment Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 235000019241 carbon black Nutrition 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 3
- 229940018557 citraconic acid Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 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 2
- HNMCSUXJLGGQFO-UHFFFAOYSA-N hexaaluminum;hexasodium;tetrathietane;hexasilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].S1SSS1.S1SSS1.[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] HNMCSUXJLGGQFO-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000001261 hydroxy acids Chemical group 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 235000019239 indanthrene blue RS Nutrition 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920001427 mPEG Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- PVIQSDYZOCWZJD-UHFFFAOYSA-N (1-tert-butylcyclohexyl) but-2-enoate Chemical compound CC=CC(=O)OC1(C(C)(C)C)CCCCC1 PVIQSDYZOCWZJD-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- AZXGXVQWEUFULR-UHFFFAOYSA-N 2',4',5',7'-tetrabromofluorescein Chemical compound OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 AZXGXVQWEUFULR-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MQFDMZNZEHTLND-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]benzoic acid Chemical compound CC(C)(C)OC1=CC=CC=C1C(O)=O MQFDMZNZEHTLND-UHFFFAOYSA-N 0.000 description 1
- QNHJNHYNHBMBLX-UHFFFAOYSA-N 2-hydroxybutyl but-2-enoate Chemical compound CCC(O)COC(=O)C=CC QNHJNHYNHBMBLX-UHFFFAOYSA-N 0.000 description 1
- UBYWYEGPDNYPHZ-UHFFFAOYSA-N 2-hydroxyethyl but-2-enoate Chemical compound CC=CC(=O)OCCO UBYWYEGPDNYPHZ-UHFFFAOYSA-N 0.000 description 1
- GWSQQDUFKKYTCA-UHFFFAOYSA-N 2-hydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCC(C)O GWSQQDUFKKYTCA-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- DOSHPXXNVROXMG-UHFFFAOYSA-N 3-hydroxybutyl but-2-enoate Chemical compound CC=CC(=O)OCCC(C)O DOSHPXXNVROXMG-UHFFFAOYSA-N 0.000 description 1
- FKMPFWRSYRKMSI-UHFFFAOYSA-N 3-hydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCCCO FKMPFWRSYRKMSI-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- BVVBDOGXOITVSY-UHFFFAOYSA-N 4-hydroxybutyl but-2-enoate Chemical compound CC=CC(=O)OCCCCO BVVBDOGXOITVSY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000532370 Atla Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RHBSFRJHUKZBLV-UHFFFAOYSA-N COCCCOC(=O)C=CC Chemical compound COCCCOC(=O)C=CC RHBSFRJHUKZBLV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- HQODYWHDMASLQN-UHFFFAOYSA-N O1C=COC=C1.N1=NN=CC=C1 Chemical compound O1C=COC=C1.N1=NN=CC=C1 HQODYWHDMASLQN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
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- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- YRJYANBGTAMXRQ-UHFFFAOYSA-N pyrazolo[3,4-h]quinazolin-2-one Chemical compound C1=C2N=NC=C2C2=NC(=O)N=CC2=C1 YRJYANBGTAMXRQ-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QHSPZGZEUDEIQM-UHFFFAOYSA-N tert-butyl but-2-enoate Chemical compound CC=CC(=O)OC(C)(C)C QHSPZGZEUDEIQM-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- NZFNXWQNBYZDAQ-UHFFFAOYSA-N thioridazine hydrochloride Chemical compound Cl.C12=CC(SC)=CC=C2SC2=CC=CC=C2N1CCC1CCCCN1C NZFNXWQNBYZDAQ-UHFFFAOYSA-N 0.000 description 1
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
本发明涉及一种包含颜料和分散剂树脂的固体颜料制剂,其中该组合物包含至少35重量%的至少一种颜料和至多65重量%的分散剂树脂,基于颜料和分散剂树脂的组合重量计算,其中该分散剂树脂包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架并且其中该制剂内的颜料颗粒具有的平均粒度为50-5,000nm。
Description
本发明涉及包含颜料和分散剂树脂的固体颜料制剂、制备颜料制剂的方法以及分散剂树脂的应用。
欧洲专利EP 1026178描述了包含颜料和分散剂树脂的可泵送和可流动的含水颜料制剂,其中分散剂树脂包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架。还描述了一种固体颜料制剂,其要求分散,即高剪切力,以制备液体含水组合物。
国际专利申请WO 96/14347涉及一种包含乙烯基单体和二羧酸二酯的交替单元的共聚物,其中酯化基团中的至少一个包含聚醚基团,所述共聚物具有的酸值小于1。还描述了包含该共聚物的液体颜料分散体和用该分散体配制的涂料组合物。
已知的液体颜料制剂通常必须用其他助剂如干壳抑制剂、防冻性增强剂、增稠剂和防结皮剂配制,以进行稳定。水基颜料制剂通常不适合溶剂性涂料组合物。液体颜料制剂中有机助溶剂的存在是不希望的,因为这些助溶剂将挥发性有机化合物引入水性涂料组合物中。EP 1026178中所述的固体粉状颜料制剂不能没有额外分散步骤而直接引入漆配制剂中。因此,它们不适合作为拌合型(stir-in)颜料。拌合型颜料制剂通常是干燥的,通常呈粉状的颜料浓缩物,其包含颜料和分散剂并且可以通过简单搅拌而无需额外分散步骤地掺入基体如涂料组合物中,因此得名拌合型颜料制剂。
需要可以在颜色性能和分散性方面与液体配制剂相当,但不要求所述额外助剂且更易处理的新颜料制剂。
因此,本发明寻求提供一种包含颜料和分散剂树脂的颜料制剂,其可以用作拌合型颜料制剂,得到具有稳定分散的颜料的漆。该颜料制剂应易于掺入其中颜料稳定分散的涂料组合物中。此外,应可以用宽范围的颜料制备颜料制剂。该颜料制剂应允许制备具有优异性能和稳定性的漆,尤其在难以分散和稳定的颜料情况下。该颜料制剂应适于着色水性和溶剂性涂料组合物。
本发明现在提供了一种包含颜料和分散剂树脂的固体颜料制剂,其中该组合物包含至少35重量%的至少一种颜料和至多65重量%的分散剂树脂,基于颜料和分散剂树脂的组合重量计算,其中该分散剂树脂包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架并且其中该制剂内的颜料颗粒具有的平均粒度为50-5,000nm。
应注意的是美国专利US 3385808描述了用于着色塑料的自由流动性非水细碎组合。这些组合由10-80重量%颜料和90-20重量%通过可聚合乙烯基化合物和聚环氧烷的自由基聚合制备的接枝聚合物组成。聚合产物通过在聚环氧烷上接枝可聚合乙烯基化合物而生产。接枝反应产生包含通过链式聚合反应产生的具有侧挂聚合物侧基的亲水性聚环氧烷骨架的树脂。
本发明的颜料制剂可以用作拌合型颜料,即它可以容易地掺入其中颜料稳定分散的涂料组合物中。此外,可以用宽范围的颜料制备颜料制剂。该颜料制剂允许制备具有优异性能和稳定性的漆,尤其在难以分散和稳定的颜料情况下。额外的优点是该颜料制剂适于着色水性和溶剂性涂料组合物。
本发明的颜料制剂可以包含无机或有机颜料。或者该颜料制剂可以包含多种不同的颜料,例如两种或更多种无机颜料,两种或更多种有机颜料,或者一种或多种无机颜料和一种或多种有机颜料的混合物。
如上所述,制剂内的颜料颗粒以细碎形式存在,即平均粒度为50-5,000nm。优选平均粒度为至少80nm,更优选至少100nm。优选平均粒度至多为3,000nm,更优选至多1,500nm,最优选至多1,000nm。颜料颗粒在该制剂中的平均粒度例如可以通过电子显微法测定。因为颜料在该制剂内的平均粒度基本与颜料搅入液体中之后的平均粒度相同,因此还可以将该颜料制剂与液体介质混合并通过动态光散射测定平均颜料粒度。
有机颜料通常为有机彩色和黑色颜料。无机颜料同样可以为有色颜料(彩色、黑色和白色颜料)以及光泽颜料和通常用作填料的无机颜料。
下列为合适的有机有色颜料的实例:
单偶氮颜料:C.I.颜料棕25;C.I.颜料橙5、13、36、38、64、67和74;C.I.颜料红1、2、3、4、5、8、9、12、17、22、23、31、48:1、48:2、48:3、48:4、49、49:1、51:1、52:1、52:2、53、53:1、53:3、57:1、58:2、58:4、63、112、146、148、170、175、184、185、187、191:1、208、210、245、247和251;C.I.颜料黄1、3、62、65、73、74、97、120、151、154、168、181、183和191;C.I.颜料紫32;
重氮颜料:C.I.颜料橙16、34、44和72;C.I.颜料黄12、13、14、16、17、81、83、106、113、126、127、155、170、174、176、180和188;
重氮缩合颜料:C.I.颜料黄93、95和128;C.I.颜料红144、166、214、220、221、242和262;C.I.颜料棕23和41;
三苯并[cd,Jk]芘-5,10-二酮颜料:C.I.颜料红168;
蒽醌颜料:C.I.颜料黄147、177和199;C.I.颜料紫31;
蒽素嘧啶颜料:C.I.颜料黄108;
喹吖啶酮颜料:颜料橙48和49;C.I.颜料红122、202、206和209;C.I.颜料紫19;
喹诺酞酮颜料:C.I.颜料黄138;
二酮吡咯并吡咯颜料:C.I.颜料橙71、73和81;C.I.颜料红254、255、264、270和272;
二噁嗪颜料:C.I.颜料紫23和37;C.I.颜料蓝80;
黄烷士酮颜料:C.I.颜料黄24;
阴丹酮颜料:C.I.颜料蓝60和64;
二氢异吲哚颜料:C.I.颜料橙61和69;C.I.颜料红260;C.I.颜料黄139和185;
异吲哚啉酮颜料:C.I.颜料黄109、110和173;
异宜和蓝酮颜料:C.I.颜料紫31;
金属配合物颜料:C.I.颜料红257;C.I.颜料黄117、129、150、153和177;C.I.颜料绿8;
紫环酮(perinone)颜料:C.I.颜料橙43;C.I.颜料红194;
苝系颜料:C.I.颜料黑31和32;C.I.颜料红123、149、178、179、190和224;C.I.颜料紫29;
酞菁颜料:C.I.颜料蓝15、15:1、15:2、15:3、15:4、15:6和16;C.I.颜料绿7和36;
皮蒽酮颜料:C.I.颜料橙51;C.I.颜料红216;
吡唑喹唑啉酮颜料:C.I.颜料橙67;C.I.颜料红251;
硫靛颜料:C.I.颜料红88和181;C.I.颜料紫38;
三芳基碳鎓颜料:C.I.颜料蓝1、61和62;C.I.颜料绿1;C.I.颜料红81、81:1和169;C.I.颜料紫1、2、3和27;C.I.颜料黑1(苯胺黑);C.I.颜料黄101(醛连氮黄);C.I.颜料棕22。
合适的无机有色颜料的实例为:
白色颜料:二氧化钛(C.I.颜料白6)、锌白、颜料级氧化锌;硫化锌、锌钡白;
黑色颜料:氧化铁黑(C.I.颜料黑11),铁锰黑,尖晶石黑(C.I.颜料黑27);碳黑(C.I.颜料黑7);
彩色颜料:氧化铬,水合氧化铬绿;铬绿(C.I.颜料绿48);钴绿(C.I.颜料绿50);群青绿;钴蓝(C.I.颜料蓝28和36;C.I.颜料蓝72);群青蓝;锰蓝;群青紫;钴紫;锰紫;氧化铁红(C.I.颜料红101);硫硒化镉(C.I.颜料红108);硫化铈(C.I.颜料红265);钼铬红(C.I.颜料红104);群青红;氧化铁棕(C.I.颜料棕6和7),混合棕,尖晶石相和刚玉相(C.I.颜料棕29、31、33、34、35、37、39和40),铬钛黄(C.I.颜料棕24),铬橙;硫化铈(C.I.颜料橙75);氧化铁黄(C.I.颜料黄42);镍钛黄(C.I.颜料黄53;C.I.颜料黄157、158、159、160、161、162、163、164和189);尖晶石相(C.I.颜料黄119);硫化镉和硫化镉锌(C.I.颜料黄37和35);铬黄(C.I.颜料黄34);钒酸铋(C.I.颜料黄184)。
通常用作填料的无机颜料的实例是透明二氧化硅、研磨的石英、氧化铝、氢氧化铝、天然云母、天然和沉淀白垩、滑石、粘土和硫酸钡。
光泽颜料是具有单相或多相结构的片状颜料,其颜色变换因干涉、反射和吸收现象的相互作用而显著。实例是铝片和铝、氧化铁以及带有一种或多种涂层,尤其是金属氧化物涂层的云母片。
如上所述,本发明的颜料制剂包含颜料和散剂树脂作为基本成分,其中该组合物包含至少35重量%的至少一种颜料和至多65重量%的分散剂树脂,基于颜料和分散剂树脂的组合重量计算。当制剂中的颜料为碳黑时,优选碳黑在颜料制剂中的含量位于所述范围的较低部分。因此,当颜料为碳黑时,颜料制剂优选包含至少40重量%,更优选至少45重量%碳黑和至多60重量%,优选至多55重量%分散剂树脂,基于颜料和分散剂树脂的组合重量计算。使用其他颜料时,颜料制剂通常包含至少60重量%,优选至少64重量%,更优选至少68重量%,最优选至少70重量%至少一种颜料和至多40重量%,优选至多36重量%,更优选至多32重量%,最优选至多30重量%分散剂树脂,基于颜料和分散剂树脂的组合重量计算。在特别优选的实施方案中,在基于颜料制剂的总重量计算时颜料和分散剂树脂的上述重量比也适用。
颜料制剂可以进一步包含常用于颜料制剂中的其他成分、添加剂或助剂,如润湿剂、消泡剂、热稳定剂、光稳定剂、抗氧化剂和其他颜料分散助剂和/或表面活性剂。脂肪乙氧基化物可以作为可以额外存在于颜料制剂中的合适表面活性剂具体提到。脂肪乙氧基化物是脂肪酸、脂肪醇、脂肪胺或脂肪酰胺基乙氧基化物。已经发现它们具有进一步改善颜料制剂的拌合性能如颜色产生速度和色强度的潜力。合适的脂肪乙氧基化物的实例是购自Akzo Nobel Surface Chemistry的BermodolSPS2525,一种椰油单乙醇酰胺乙氧基化物。脂肪乙氧基化物可以类似于或甚至超过分散剂树脂量的量存在。
在一个实施方案中,本发明的颜料制剂是适合用作拌合型颜料的自由流动粉末。此外,固体压实颜料制剂例如可以丸粒或片的形式使用。
要用于本发明颜料制剂和方法中的分散剂的聚合物骨架可以通过合适的烯属不饱和可聚合单体的链式聚合反应而制备。
合适的链式聚合反应的实例是众所周知的上述烯属不饱和可聚合单体的自由基聚合。聚合可以分一步或多步且在有机稀释剂存在或不存在下进行。
合适的形成自由基的引发剂在本领域是已知的,如过氧化二叔丁基、过氧苯甲酸叔丁基酯、过氧-2-乙基己酸叔丁基酯、过氧-3,5,5-三甲基己酸叔丁基酯等以及偶氮引发剂如2,2′-偶氮二(2-甲基丁腈)和2,2′-偶氮二(异丁腈)。
聚合物的分子量可以通过链转移剂如正辛基硫醇、正十二烷基硫醇、叔十二烷基硫醇、巯基乙醇、巯基丙酸或巯基乙醇控制。
聚合物骨架的聚合度,即每个聚合物骨架的单体平均数,合适地为5-150,优选10-100,更优选15-50。
也可以将高级聚合技术,如基团转移聚合(GTP)、氮氧调控聚合(NMP)、原子转移自由基聚合(ATRP)和可逆加成断裂链转移(RAFT)聚合用于制备该聚合物骨架。
对制备聚合物骨架合适的单体是烯属不饱和可聚合单体。该类单体的合适实例是在醇部分中具有1-18个碳原子的丙烯酸酯或甲基丙烯酸酯,如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙基酯、(甲基)丙烯酸正丁基酯、(甲基)丙烯酸异丁基酯、(甲基)丙烯酸叔丁基酯、(甲基)丙烯酸己基酯、(甲基)丙烯酸环己基酯、(甲基)丙烯酸正辛基酯、(甲基)丙烯酸正癸基酯、(甲基)丙烯酸异癸基酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸3,5,5-三甲基环己基酯、(甲基)丙烯酸叔丁基环己基酯、(甲基)丙烯酸异冰片基酯、(甲基)丙烯酸硬脂基酯,具有醚基的(甲基)丙烯酸酯,如(甲基)丙烯酸2-甲氧基乙基酯、(甲基)丙烯酸2-乙氧基乙基酯和(甲基)丙烯酸3-甲氧基丙基酯;(甲基)丙烯酸2-羟基丁基酯、(甲基)丙烯酸3-羟基丁基酯,或优选(甲基)丙烯酸2-羟基乙基酯、(甲基)丙烯酸2-羟基丙基酯、(甲基)丙烯酸3-羟基丙基酯以及(甲基)丙烯酸4-羟基丁基酯,(甲基)丙烯酸,乙基丙烯酸(ethacrylic acid),丙烯酸β-羧基乙基酯,巴豆酸、马来酸、富马酸、衣康酸、柠康酸,不饱和二元酸如马来酸、衣康酸和柠康酸的单烷基酯;其他甲基丙烯酸酯如甲基丙烯酸二甲氨基乙基酯、(甲基)丙烯酸缩水甘油基酯、甲基丙烯酸2-乙酰乙酰氧基乙基酯和甲基丙烯酸3-(三甲氧基甲硅烷基)丙基酯。其他合适的单体是在醇部分中具有1-18个碳原子的丙烯酸β-羧基乙基酯和巴豆酸的酯以及在(环)烷基中具有1-12个碳原子的不饱和二羧酸的(环)烷基酯,如马来酸二乙酯和富马酸二丁酯、衣康酸二(环)烷基酯和柠康酸二(环)烷基酯。
其他合适的烯属不饱和单体包括乙烯基芳族化合物如苯乙烯,α-甲基苯乙烯,邻-、间-或对-甲基苯乙烯和叔丁基苯乙烯;马来酸酐,衣康酸酐,柠康酸酐,丙烯酰胺,甲基丙烯酰胺,丙烯腈,N-烷氧基丙烯酰胺,N-烷氧基甲基丙烯酰胺;C1-C18单羧酸的乙烯基酯如乙酸乙烯酯、丙酸乙烯酯、异丁酸乙烯酯,α-支化C5-C18单羧酸的乙烯基酯。其他合适的乙烯基单体包括氯乙烯、偏二氯乙烯、乙烯基吡咯烷酮以及乙烯基硅烷如乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷。
聚合物骨架还可以含有少量直至约10%的多不饱和单体如甲基丙烯酸烯丙基酯、乙二醇二甲基丙烯酸酯、己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯等的聚合单元。
分散剂树脂具有至少一个由聚合物骨架侧挂的聚环氧烷侧基。优选分散剂树脂具有两个或更多个侧挂聚环氧烷侧基。具有3-20个聚环氧烷侧基的分散剂树脂特别合适。侧挂聚环氧烷侧基的数目通常不超过100。在典型实施方案中,该树脂的聚合物骨架基本为线性且具有侧挂亲水性聚环氧烷侧基。该类聚合物也可以描述为梳型聚合物。
至少一个侧挂亲水性聚环氧烷侧基可以通过在聚合反应中使用具有至少一个聚环氧烷基团的单体引入。该类单体的实例是聚(乙二醇)甲基醚丙烯酸酯和聚(乙二醇)甲基醚甲基丙烯酸酯。
或者可以在后聚合反应中引入至少一个侧挂亲水性聚环氧烷基团,即首先制备聚合物骨架,然后将至少一个侧挂亲水性聚环氧烷基团接枝到该骨架上。此时优选将具有对后聚合反应合适的官能基团的单体包括在聚合物骨架中。该类官能基团的实例是羟基、乙酰乙酰氧基、羧酸基团、环状羧酸酐基团、异氰酸酯基团、环氧化物基团等。特别优选环状羧酸酐基团。包含环状羧酸酐基团的烯属不饱和可聚合单体的实例是马来酸酐、衣康酸酐和柠康酸酐,优选马来酸酐。马来酸酐和苯乙烯的共聚物是特别优选的聚合物骨架。
为了通过后聚合反应引入至少一个侧挂亲水性聚环氧烷基团,特别合适的是通过如下组分的反应制备颜料分散剂树脂:
(i)下式的亲水性聚环氧烷单胺单烷基醚:
其中R为烷(烯)基或优选为氢,R1选自C1-C4烷基,n为0-25,m为1-50,条件是n+m≤50,和
(ii)具有环状羧酸酐基团的聚合物骨架。
亲水性聚环氧烷单胺单烷基醚与聚合物骨架的环状羧酸酐基团反应。在该反应中,环状羧酸酐首先由亲水性聚环氧烷单胺单烷基醚的胺基打开而形成酰胺基团和羧酸基团(酰胺酸基团)。在该步骤中亲水性聚环氧烷基团已经连接于聚合物骨架且产物可以在本发明颜料制剂中用作分散剂树脂。当式(I)中的R为氢时,酰胺酸基团还可以在第二反应步骤中进行缩合反应以形成酰亚胺。优选至少部分酰胺酸基团形成酰亚胺。
分散剂树脂的聚环氧烷含量合适地为至少20重量%,优选至少35重量%,更优选至少50重量%,最优选至少65重量%,基于该分散剂树脂的总重量计算。该分散剂树脂的聚环氧烷含量的合适上限为95重量%,优选90重量%,更优选85重量%,基于该分散剂树脂的总重量计算。
合适的氧化烯实例是氧化乙烯、氧化丙烯和氧化丁烯。优选聚环氧烷基侧基基于氧化乙烯或氧化丙烯或其混合物。基于聚环氧烷基侧基的总重量计算,聚环氧烷基侧基至少50重量%,优选70重量%基于氧化乙烯时得到非常好的结果。聚环氧烷基侧基通常具有的分子量为至少200,优选至少350,最优选至少700。聚环氧烷基侧基的分子量通常不超过4,000,优选不超过3,000。
分散剂树脂任选包含离子性基团。离子性基团的实例是阴离子基团,如碱中和的酸性基团,以及阳离子基团,如酸中和的碱性基团。离子性基团可以通过在聚合物骨架的制备中使用合适的单体而引入。合适单体的实例是羧酸和/或羧酸酐官能单体,如丙烯酸和马来酸酐。
若分散剂树脂的聚环氧烷含量在上述范围的较低端,则特别优选存在离子性基团,以确保颜料制剂的所需性能。作为已中和和未中和酸性基团的总和计算的分散剂树脂的酸值合适地为0-200mg KOH/g,基于分散剂树脂的非挥发物质计算。优选酸值至少为5mg KOH/g,更优选至少15mgKOH/g。优选酸值小于150mg KOH/g,更优选小于100mg KOH/g,最优选小于50mg KOH/g。
分散剂树脂的数均分子量合适地为至少1,500,优选至少3,000,更优选至少8,000,最优选至少12,000。分散剂树脂的数均分子量合适的是小于150,000,优选小于100,000,更优选小于60,000,最优选小于40,000。
本发明进一步涉及一种制备颜料制剂的方法,包括如下步骤:
a)搅拌颜料和分散剂树脂以及任选加入的水或有机稀释剂,形成流化颜料淤浆,
b)任选研磨该淤浆,和
c)干燥该淤浆,
其中分散剂树脂包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架。
如上面对颜料制剂所述,用于该方法中的颜料可以是有机或无机颜料。还可以使用颜料混合物,例如两种或更多种无机颜料的混合物,两种或更多种有机颜料的混合物或无机和有机颜料的混合物。可以在该方法中使用大量颜料。可以将颜料以标准干燥颜料引入该方法中。研磨步骤用于打碎附聚体并实现所需颜料粒度。有机颜料还可以所谓的滤饼提供。有机颜料在合成时呈非常小的晶体形式,其被称为初级粒子。颜料合成的目的是产生其尺寸能够优化颜料应用性能如色强度、色泽和亮度、透明性和不透明性以及流动性能的初级粒子。滤饼含有的颜料基本呈这种解聚形式。因此,打碎附聚体和实现所需颜料粒度要求较少的能量。在颜料滤饼在没有分散剂树脂存在下的干燥过程中,初级粒子将结合在一起形成聚集体并附聚。因此,当将有机颜料用于该方法中时,可以且优选使用颜料滤饼形式的有机颜料。当使用颜料滤饼时,流化颜料淤浆的简单搅拌可能就足以实现所需颜料粒度。在这类情形下淤浆的研磨可能是多余的。
当要求额外液体来流化颜料和分散剂树脂的混合物时,优选该液体为水。代替水或除了水以外,可以使用有机溶剂,如二醇或二醇醚,例如乙二醇或其高级同系物或乙二醇单正丁基醚。
任选的研磨步骤可以使用常用于降低颜料粒度的众所周知的研磨设备进行。适于进行该方法的设备实例是珠磨机、喷射磨、超声磨机、篮式磨机、辊磨机和高速溶解器。研磨通常继续到平均粒度为50-5,000nm为止。优选平均粒度为至少80nm,更优选至少100nm。优选平均粒度为至多3,000nm,更优选至多1,500nm,最优选至多1,000nm。
合适的干燥方法实例是喷雾造粒和流化床干燥、喷雾干燥、在桨叶干燥器中干燥、蒸发和随后粉碎以及冷冻干燥。选定的干燥方法可能影响本发明颜料制剂的粒度。干燥步骤优选通过冷冻干燥或喷雾干燥进行。
喷雾和流化床造粒可以产生平均粒度为50-5,000μm,尤其是100-1,000μm的粗碎颗粒。取决于工艺条件,喷雾干燥也可以产生细碎颜料制剂。喷雾干燥可以产生平均粒度<20μm的颗粒。也可以通过在桨叶干燥器中干燥和通过蒸发并随后研磨而得到细碎制剂。
所得干燥的颜料制剂的残留水分含量可以显著变化。残留水分含量例如可以为15重量%,基于整个颜料制剂的重量计算。残留水分含量通常不超过15重量%,优选不超过12重量%。在许多情况下,残留水分含量甚至低于5重量%。当要将颜料制剂用于非水体系时,特别优选低残留水分含量,例如低于2重量%。
本发明的颜料制剂在使用中以其优异的颜色性能,尤其是色强度、亮度、色调和遮盖力以及尤其是它们的拌合特性著称,即它们可以简单地通过搅拌或振摇而以最小能量输入分散在应用介质中。
本发明的颜料制剂额外具有下列优点:它们具有高颜料含量,呈现非常良好的储存稳定性,对于包装、储存和运输在经济和生态上均有利,并且它们在使用中更灵活,即它们可以用于着色水性组合物和溶剂性组合物。
本发明的颜料制剂对于任何种类的大分子有机和无机材料的着色非常有用。就此而言,液体应用介质可以是纯粹水性的,包含水和有机溶剂如醇的混合物,或者可以仅基于有机溶剂如醇、二醇醚、酮如甲基乙基酮、酰胺如N-甲基吡咯烷酮和二甲基甲酰胺、酯如乙酸乙酯、乙酸丁酯和乙酸甲氧基丙基酯,或芳族或脂族烃类如二甲苯、矿物油和石油溶剂油。
可以用本发明的颜料制剂着色的材料实例包括:涂料,例如建筑涂料、工业涂料、汽车涂料、可辐射固化的涂料;粉末涂料;漆,包括建筑外用漆和建筑内用漆,例如木漆、石灰水浆涂料、刷墙水浆涂料、乳胶漆;溶剂性印刷油墨,例如胶印油墨、柔性版印刷油墨、甲苯凹版印刷油墨、织物印刷油墨、可辐射固化印刷油墨;水性油墨,包括喷墨油墨;滤色片;建筑材料(通常仅在将建筑材料和颜料制剂干混之后加入水),例如硅酸盐打底体系、水泥、混凝土、灰浆、石膏;沥青、嵌缝胶;纤维素材料,例如纸张、纸板、卡纸板、木材和木制品,它们可以各自被涂敷或涂饰;粘合剂;例如用于药物工业的成膜聚合物保护胶体;化妆制品;塑料;以及洗涤剂。
本发明的颜料制剂尤其可以在混色或配色体系中用作混合组分。由于它们的拌合特性,它们可以直接以固体用于该目的。然而,需要的话还可以将它们首先转化成基础色料、配漆用漆料和着色色料(尤其转化成具有高固体含量的色料,“HS色料”),或者甚至更高度着色的着色浆,它们又构成混合体系的组分。所需色调的匹配以及因此色料组分的混合可以经由色卡系统在非常大量的基于色标如RAL、BS和NCS的色调梯度中肉眼进行,或者优选在计算机控制下进行,由此可以得到无限数目的色调(“计算机配色”)。制备着色的涂料组合物的方法包括以任何可操作的顺序搅拌混合本发明的颜料制剂、至少一种成膜基料和至少一种液体稀释剂。
实施例
所用原料:
马来酸酐的摩尔比为2/1,购自Cray Valley
脂分散体的共混物,购自Akzo Nobel Car
Refinishes
体,购自Akzo Nobel Car Refinishes
Refinishes
Refinishes
通用方法:
组合物的固体含量通过在将样品加热到140℃并保持30分钟后测量重量损失而确定。
分子量通过使用聚苯乙烯作为标准的尺寸排阻色谱法测定。
光泽度使用Byk-Gardner光泽计测定,结果以光泽单位报道。
色度(C*)值根据CIE LCh体系测定。
实施例1
制备具有聚合物骨架和侧挂亲水性聚环氧烷侧基的分散剂树脂
在配有搅拌器、热电偶、加热夹套、回流冷凝器和滴液漏斗的反应容器中放入20.3重量份SMA 2000和79.7重量份JeffamineM 2070。将该混合物在真空下加热到180℃。蒸除反应水并在180℃下继续反应,直到酸值小于30mg KOH/g。然后将反应混合物冷却至室温。该分散剂树脂可溶于水中,酸值为28.0mg KOH/g(基于非挥发物计算),数均分子量为17,100且重均分子量为43,000。
实施例2
制备本发明的颜料制剂
制备33.5重量份实施例1的分散剂树脂的40%水溶液、20.1重量份软化水、0.3重量份市售消泡剂、0.5重量份二甲基乙醇胺和45.6重量份IrgazinDPP Red BO颜料的混合物。
使用ECM导向磨铣器以7升的规模珠磨该混合物并使用0.7-0.9mm珠粒将颜料分散总共75遍。平均粒度为170nm。
将样品在入口温度为132℃且出口温度为85℃的Büchi微喷雾干燥器中喷雾干燥,其中流速为0.2kg/hr。没有发现喷嘴明显堵塞或压力增加。将粉状颜料制剂干燥到约1%残留水分且计算出颜料含量为76.8%。得到的颜料制剂为自由流动干粉。
实施例3-10和对比例A-F
涂料组合物的制备
将实施例2的颜料制剂作为拌合型颜料在两种不同的水性基料体系-Autowave665(实施例3)和Autowave666(实施例4)以及两种不同的溶剂性基料体系-AutocrylPlus(实施例5)和AutocrylLV(实施例6)中测试。将带有在750-760rpm下操作的4cm搅拌桨叶的IKA RW20搅拌器用于测试。在搅拌下加入实施例2的颜料制剂,然后在设定的速度下维持总共30分钟。加入足够的颜料制剂而得到颜料含量为6.6重量%(实施例3和4)、9.58重量%(实施例5)和11.76重量%(实施例6)的涂料组合物。这些颜料含量与用作对照的对比例的那些相同:
对比例B:AutocrylPlus色料A273,实施例5的对照
得到的涂料组合物具有优异的研磨细度值且在Hegmann细度计测试中无明显颗粒。
白色稀释料通过将涂料组合物与白色调色浆混合而制备:
实施例7
将实施例3的涂料组合物与白色组合调色浆Autowave00混合,从而使所得混合物中红色颜料与白色颜料的重量比为50∶50。
实施例8
对比例D
实施例9
将实施例5的涂料组合物与白色组合调色浆AutocrylPlus A110混合,从而使所得混合物中红色颜料与白色颜料的重量比为50∶50。
对比例E
实施例10
对比例F
将对比例C的涂料组合物与白色组合调色浆AutocrylPlus S110混合,从而使所得混合物中红色颜料与白色颜料的重量比为50∶50。
使用K-控制涂布机(刮涂棒0.4,速度3)将涂料组合物施涂于LenetaForm 2A不透明板上并在室温下干燥过夜。在施涂前将实施例5、6、9、10和B、C、E和F与AutocrylLV硬化剂420以2∶1的体积比混合。
结果总结于表1中。
实施例 | 拌合性能 | 光泽度(60°) | 光泽度(20°) | 色度(C*) |
A | 不可施涂 | 64.2 | 14.4 | 69.45 |
3 | 优异 | 79.0 | 49.6 | 73.55 |
4 | 优异 | 79.3 | 51.0 | 73.60 |
B | 不可施涂 | 92.8 | 85.1 | 76.13 |
5 | 良好 | 93.3 | 86.2 | 75.49 |
C | 不可施涂 | 91.7 | 84.8 | 75.80 |
6 | 良好 | 91.8 | 85.0 | 75.59 |
D | 不可施涂 | 65.8 | 18.9 | 63.24 |
7 | 不可施涂 | 73.2 | 34.5 | 60.42 |
8 | 不可施涂 | 80.4 | 47.0 | 62.06 |
E | 不可施涂 | 92.8 | 86.6 | 58.44 |
9 | 不可施涂 | 92.4 | 84.4 | 60.52 |
F | 不可施涂 | 91.5 | 84.7 | 57.63 |
10 | 不可施涂 | 91.1 | 82.7 | 62.26 |
在所有所测试的水性底色漆和溶剂性面漆涂料中全色调颜色性能良好。在水性底色漆和溶剂性面漆中的光泽度与对照中的相当并且在某些情况下更好。
Claims (11)
1.一种包含颜料和分散剂树脂的固体颜料制剂,其中该组合物包含至少35重量%的至少一种颜料和至多65重量%的分散剂树脂,基于颜料和分散剂树脂的组合重量计算,其中所述分散剂树脂包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架,其特征在于所述制剂内的颜料颗粒具有的平均粒度为50-5,000nm。
2.根据权利要求1的颜料制剂,其特征在于聚环氧烷在所述分散剂树脂中的含量为至少20重量%。
3.根据权利要求1或2的颜料制剂,其特征在于聚环氧烷基于氧化乙烯、氧化丙烯或其混合物。
4.根据前述权利要求中任一项的颜料制剂,其特征在于所述分散剂树脂的数均分子量为1,500-150,000。
5.根据前述权利要求中任一项的颜料制剂,其特征在于所述分散剂树脂的酸值为5-150mg KOH/g。
6.根据前述权利要求中任一项的颜料制剂,其特征在于所述制剂进一步包含脂肪乙氧基化物表面活性剂。
7.一种制备颜料制剂的方法,包括如下步骤:
a)搅拌颜料和分散剂树脂以及任选加入的水或有机稀释剂,形成流化颜料淤浆,
b)任选研磨所述淤浆,和
c)干燥所述淤浆,
其中所述分散剂树脂包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架。
8.根据权利要求7的方法,其特征在于所述颜料为以滤饼形式提供的有机颜料。
9.根据权利要求7或8的方法,其特征在于步骤c)通过冷冻干燥或喷雾干燥进行。
10.一种制备着色的涂料组合物的方法,包括在搅拌下以任何可操作的顺序混合下列组分:
a.根据前述权利要求1-6中任一项的颜料制剂,
b.至少一种成膜基料,和
c.至少一种液体稀释剂。
11.包含通过链式聚合反应产生的具有侧挂亲水性聚环氧烷侧基的聚合物骨架的分散剂树脂在制备拌合型颜料制剂中的用途。
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US60/749,039 | 2005-12-12 | ||
PCT/EP2006/066985 WO2007039603A2 (en) | 2005-10-04 | 2006-10-03 | Pigment preparation |
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EP (1) | EP1940969B1 (zh) |
JP (1) | JP2009510246A (zh) |
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CN (1) | CN101283053B (zh) |
AT (1) | ATE520745T1 (zh) |
AU (1) | AU2006298645B2 (zh) |
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CN113527695A (zh) * | 2021-07-23 | 2021-10-22 | 中山市钧纬新材料科技有限公司 | 一种超支化聚合物水性分散剂的制备方法及应用 |
CN115011175A (zh) * | 2022-05-05 | 2022-09-06 | 浙江理工大学 | 一种稀土颜料光固化色浆及其制备方法 |
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2006
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108385441A (zh) * | 2018-02-12 | 2018-08-10 | 广东轻工职业技术学院 | 一种纸用阳离子纳米色浆及其制备方法和应用 |
CN113527695A (zh) * | 2021-07-23 | 2021-10-22 | 中山市钧纬新材料科技有限公司 | 一种超支化聚合物水性分散剂的制备方法及应用 |
CN115011175A (zh) * | 2022-05-05 | 2022-09-06 | 浙江理工大学 | 一种稀土颜料光固化色浆及其制备方法 |
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JP2009510246A (ja) | 2009-03-12 |
RU2008117419A (ru) | 2009-11-10 |
AU2006298645A1 (en) | 2007-04-12 |
BRPI0616802B1 (pt) | 2017-05-30 |
EP1940969B1 (en) | 2011-08-17 |
ATE520745T1 (de) | 2011-09-15 |
EP1940969A2 (en) | 2008-07-09 |
ES2371559T3 (es) | 2012-01-05 |
PL1940969T3 (pl) | 2012-01-31 |
AU2006298645B2 (en) | 2011-11-10 |
WO2007039603A3 (en) | 2007-06-07 |
RU2418829C2 (ru) | 2011-05-20 |
CN101283053B (zh) | 2012-03-21 |
US7842757B2 (en) | 2010-11-30 |
KR101358772B1 (ko) | 2014-02-11 |
BRPI0616802A2 (pt) | 2011-06-28 |
WO2007039603A2 (en) | 2007-04-12 |
US20090030139A1 (en) | 2009-01-29 |
KR20080045756A (ko) | 2008-05-23 |
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