TWI625364B - 氯化酞青銅顏料 - Google Patents
氯化酞青銅顏料 Download PDFInfo
- Publication number
- TWI625364B TWI625364B TW105117567A TW105117567A TWI625364B TW I625364 B TWI625364 B TW I625364B TW 105117567 A TW105117567 A TW 105117567A TW 105117567 A TW105117567 A TW 105117567A TW I625364 B TWI625364 B TW I625364B
- Authority
- TW
- Taiwan
- Prior art keywords
- phthalocyanine
- pigment
- pigments
- bronze
- pigment composition
- Prior art date
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 93
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 title description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 35
- 239000010974 bronze Substances 0.000 claims abstract description 35
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000001309 chloro group Chemical class Cl* 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 7
- -1 color filter Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 4
- 230000000996 additive effect Effects 0.000 claims 4
- 238000005516 engineering process Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 235000017168 chlorine Nutrition 0.000 abstract description 5
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 35
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 19
- 239000012043 crude product Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000002140 halogenating effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 6
- 229920006391 phthalonitrile polymer Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 description 3
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- HCXVRWNMKLEOKO-UHFFFAOYSA-N 2-benzofuran-1,3-dione;urea Chemical compound NC(N)=O.C1=CC=C2C(=O)OC(=O)C2=C1 HCXVRWNMKLEOKO-UHFFFAOYSA-N 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HUVXQFBFIFIDDU-UHFFFAOYSA-N aluminum phthalocyanine Chemical compound [Al+3].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HUVXQFBFIFIDDU-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- YTDHEFNWWHSXSU-UHFFFAOYSA-N 2,3,5,6-tetrachloroaniline Chemical compound NC1=C(Cl)C(Cl)=CC(Cl)=C1Cl YTDHEFNWWHSXSU-UHFFFAOYSA-N 0.000 description 1
- STQPCKPKAIRSEL-UHFFFAOYSA-N 2-cyanobenzamide Chemical compound NC(=O)C1=CC=CC=C1C#N STQPCKPKAIRSEL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LBGCRGLFTKVXDZ-UHFFFAOYSA-M ac1mc2aw Chemical compound [Al+3].[Cl-].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LBGCRGLFTKVXDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003560 cancer drug Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material 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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
-
- 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
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
-
- 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
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
- C09B67/0016—Influencing the physical properties by treatment with a liquid, e.g. solvents of phthalocyanines
-
- 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
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
- C09B67/0023—Wet grinding of pigments of phthalocyanines
-
- 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
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine 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
- C09B67/0032—Treatment of phthalocyanine 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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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Abstract
本技術的目標為克服習知產生酞青銅的酞青銅之氯化的缺點，其中氯的數目係少於或等於4。於本文中所描述的顏料包括比標準商業等級之四氯化(或較大)酞青銅顏料少的氯，同時在汽車用水載型及溶劑型系統中達成類似的色彩空間、色度、堅牢度性質及色彩傳播(color travel)。從毒性及環境視角來看，本發明的顏料更優良及允許製造商以安全及經濟的方式製造顏料。
Description
本申請案主張2015年6月4日提出的美國臨時專利申請案號62/170,756，發明名稱“Chlorinated Copper Phthalocyanine Pigments”之優先權，其全文於此以參考方式併入本文。
本發明係關於一種氯化酞青銅顏料。
酞青化合物係一種高度安定之18個π電子共軛巨環物，其具有強烈鮮明的顏色及由下列通式表示：
酞青類包括金屬-酞青配位化合物(即，M係能鍵結至酞青分子的中央腔及可具有接附軸向配位基的能力之原子)及無金屬酞青(即，M為H)，其時常使用在紡織品及紙工業中作為染料或顏料，及亦已使用作為化學感應器、光動力癌藥物、非線性光學材料、觸媒及液晶。
酞青類可在加熱酞酸衍生物諸如酞酸酐、酞醯亞胺、酞腈或鄰-氰基苯甲醯胺，與氮來源諸如尿素後形成，在此情況中，酞酸衍生物其自身不包括足夠的氮。金屬酞青配位化合物之合成額外需要存在有適當的金屬衍生物。金屬酞青通常遵循二種方法之一合成。常見的方法之一為使用酞醯亞胺或酞酸酐(如為至酞醯亞胺之前驅物)作為起始材料，同時其它方法係以酞腈開始。二者方法皆包括同時合成該配位基與形成該金屬錯合物。
通常來說，為了從酞酸酐合成金屬酞青，在高沸點溶劑中加熱酞酸酐與尿素、金屬鹵化物諸如氯化鋁(III)(AlCl3)及小量觸媒諸如鉬化合物，其中尿素作用為氮來源。在這些反應中，必需存在有觸媒以催化關鍵中間物1-胺基-3-亞胺基異-吲哚啉之形成。在使用酞酸酐作為起始材料來合成金屬酞青顏料酞青氯鋁，其係描述在下列中：Huanshun等人，”Metal phthalocyanine solid phase synthesis”，Ranliao Yu Ranse 41(3)：150-152(2004)；中國專利案號CN 101717401；日本公開案號JP 2003-176424、JP 2003-176423；日本專利案號JP 4407097；及美國專利案號6,826,001。這些程序全部包括使用催化量的鉬，典型為鉬酸銨、氧化鉬(molybdic oxide)或另一種類似的鉬化合物。
普通使用來合成金屬酞青的其它方法係以酞腈開始及包括將酞腈與金屬鹵化物諸如AlCl3加熱至約200℃，含或不含溶劑。例如，使用C1-C10醇例如乙醇作為溶劑來合成酞青氯鋁的方法僅提供68%產率(RU
2164233)；及包括於AlCl3存在下，在180℃水中加熱酞腈之方法係描述為劇烈強力及僅產生70%產率(JP 62-158284)。當該反應亦包括使用氨時，獲得更低的產率。允許在與酞腈加熱前形成氨與氯化鋁之錯合物，此產生47%產率的酞青氯鋁(JP 2000-1270885)。
除了上述二種方法外，亦可藉由取代(即，金屬轉移)反應來製備金屬酞青。例如，可從不同金屬酞青諸如酞青銅來製備酞青氯鋁。在這些反應中，該金屬(例如，銅)係藉由在熔融的AlCl3及NaCl中將酞青銅加熱至240℃六小時由鋁置換(EP 0 635 550及U.S.5,556,966)。但是，最後產物可包括未反應的酞青銅，因此引起與使用金屬觸媒製備的酞青類類似之環境關注。
已熟知酞青銅類之色蔭係根據存在於分子中的氯原子數而改變。因此，當引進8個氯原子時，未氯化的酞青銅之藍色色蔭改變成藍綠色；及當將12或更多個氯原子併入該酞青銅分子中時，其改變成更強的綠色色蔭(”酞青綠”)。
已經藉由多種方法製造出氯化金屬酞青。液體鹵化劑包括硫醯氯及亞硫醯氯。此鹵素試劑如氯化鋁係以限制量使用，但是整體反應媒質由該液體鹵化劑組成。換句話說，該鹵化劑係與供應該用於反應的液體媒質相依。
用以製備酞青綠的典型程序使用大量昂貴的試劑諸如氯磺酸作為溶劑，然後，其在反應完成後丟棄。由於丟棄溶劑的浪費及製得該氯化酞青類需要長的反應時間二者，此方法昂貴。
Moser及Thomas，Phthalocyanine Compounds，第172-179頁，Reinhold Publishing Corporation，紐約(1963)揭示出使用氯化銅作為用以氯化酞青銅的觸媒。但是，其未揭示出在包括酞青銅與硫醯氯反應之方法中使用氯化銅。
美國專利案號3,320,276教導於氯化鋁及/或溴化鋁存在下，硫醯氯將沒有加入元素態鹵素而鹵化無金屬酞青或酞青的金屬錯合物諸如酞青銅，及較佳為包括存在有鹼金屬鹵化物諸如氯化鈉與單氯化硫作為鹵素載劑。但是，此方法需要該氯化鋁或溴化鋁呈熔融流體形式。此具有許多缺點，因為其需要用以加熱及將氯化鋁維持在流體狀態的設備。在此方法中需要大量氯化鋁，例如，對10份酞青銅來說，全部實施例需要100份無水氯化鋁。再者，要丟棄水解的氯化鋁(在反應結束時)及此可促成污水問題。
通常來說，酞青已經藉由酞青當其溶解在氯化鋁與氯化鈉的共熔鹽中時進行鹵化之方法，或酞青當其溶解在氯磺酸中時進行鹵化之方法進行工業上鹵化。但是，在這些方法中，回收溶劑在工業上有困難，結果，造成大量酸性污水。為了環境保護，該污水應該經處理及該處理需要龐大費用。至於為了妥善處理上述問題而使用可回收的溶劑之鹵化方法，已經揭示出使用金屬氯化物作為溶劑的方法。例如，JP-A-52-29819及美國專利4,948,884揭示出一種在四氯化鈦作為溶劑中鹵化酞青的方法。
對有效率合成最低限度氯化的酞青顏料及顏料組成物之方法存在有需求，諸如最低限度氯化的金屬酞青顏料，其中氯原子數目係少於4，及亦最低限度氯化的酞青銅顏料，其中在該顏料組成物中的平均氯數目為1，因此最小化負面環境衝擊。
本技術的目標為克服習知氯化金屬酞青之缺點，及製備包括比至少四氯化較少氯原子之金屬(銅)酞青，酞青銅顏料。本技術係有關包括比標準四氯化酞青銅顏料較少氯之顏料，其主要呈β相，同時在汽車用水載型及溶劑型系統中提供類似的色彩空間、色度、堅牢度性質及色彩傳播(color travel)。從毒性及環境視角(environmental perspective)來看，這些顏料更優良，及允許製造商以安全及經濟方式製造顏料。
圖1：氯化酞青銅(m=0.71；n=0.29)-在實施例1中的”粗產物#1”之X射線繞射圖案。
圖2：氯化酞青銅(m=0.60；n=0.40)-在實施例2中的”粗產物#2”之X射線繞射圖案。
本技術係關於一種呈β結晶形式及通式(I)的氯化酞青銅顏料，其中β結晶形式係此顏料的主要相，其中該取代程度係由下列表示：0.4<m+n4
mn
n>0.2
其中m代表在α位置處的平均氯取代基數目，及n代表在β位置處的平均氯取代基數目。
該氯化酞青銅顏料平均可包括1個氯原子，諸如單氯化酞青銅顏料。已認為這些氯化酞青顏料比包含至少4個氯原子的高氯化酞青顏料較安全、較少毒性及引起較少環境衝擊。在本技術中的顏料係混合的結晶形式，大部分為α及β形式及主要為β形式。該β結晶形式係主要相，其包含該結晶形式的至少50%。如與標準(四氯化及較大)酞青銅顏料比較，這些顏料在汽車用塗料系統中引起類似的色彩空間、色度、耐光性及色彩傳播。
本氯化酞青銅顏料可藉由現存的酞青合成程序製備及提供顏料製造商更成本有效的方法，以製備出具有類似於標準四氯酞青銅顏料的性質之顏料產物而沒有與處理及使用氯氣相關的供應及資本投資。
用以合成這些氯化酞青銅顏料的較佳方法為酞酸酐-尿素方法(Wyler方法)，但是該合成不限於任何特別的方法。該氯化酞青銅顏料顆粒尺寸及形狀可由合
成方法、在合成步驟期間的反應媒質之選擇、及隨後的完成步驟(例如，熱壓消毒、鹽磨(salt attrition)、球磨、酸膨脹(acid swelling)等等)影響。
使用Siemens D5000繞射儀與石墨單色Cu Kα1輻射(λ=1.5406埃)獲得X射線粉末繞射圖案。將該粉末顏料樣品緊緊地裝填在2”×2”標準樣品支架中。然後，將該樣品支架負載至X射線繞射儀用以分析。使用來自Bruker AXS，Inc.的石英標準物(P/N C72298A227B36)校正儀器。該X射線繞射波峰經了解係在實驗界限內及可產生稍微不同的波峰。亦要了解的是，其它測試方法可產生不同波峰。表1及2總整理出如在實施例1及2中產生之”粗產物#1”及”粗產物#2”的X射線繞射圖案，其中該等粗產物係從該反應產生之全部可能的氯化酞青銅化合物之複雜的混合結晶。提供在表中的值係具有相對強度5%及d2.5埃之那些。圖1及2闡明X射線繞射圖案。
於此提供的方法產生一平均酞青銅顏料組成物，其係單氯化及該β結晶形式係主要相。該單氯化顏料組成物可合適於塗佈物(諸如汽車用塗料)、塑膠、印刷油墨、水載型或溶劑型顏料製劑、電子照像色劑及顯色劑、粉末塗佈材料、油墨較佳為噴墨油墨、濾色片及著色種子(coloring seed)。
亦可在此技術的範圍內包括酞青衍生物及包含顏料顆粒。酞青衍生物包括但不限於酞青磺醯胺類、酞醯亞胺基甲基酞青、烷氧基化酞青衍生物、酞青磺酸類(“磺酸化的酞青”)及其鹽。
本技術已經詳細地描述，包括其較佳具體實例。但是，將察知的是，熟習該項技術者在考慮本揭示後可於此技術上修改及/或改良，且其落在本技術之範圍及精神內。
下列實施例闡明本技術的特定態樣，但不意欲在任何方面限制其範圍，且不應該被如此解。
這些實施例描述出此技術的組成物之製備及使用。藉由X射線繞射(Siemens D5000繞射儀)分析根據這些實施例所製備的顏料。用以合成這些氯化酞青銅顏料的較佳方法為酞酸酐-尿素方法(Wyler方法)與二鉬酸銨觸媒。
如於本文中所使用，用語”顏料/顏料的”指為在從反應混合物分離出後，已經處理或進一步加工，以發展出必要的顏料性質之酞青反應產物，諸如例如，顆粒尺寸，諸如在約20奈米至90奈米間或在約30至70奈米間之顆粒尺寸分佈；顆粒形狀、結晶結構、團聚、多形相及著色力。該處理或進一步加工酞青反應產物以獲得顏料性酞青產物可包括研磨、輪磨或純化、或其任何組合。
藉由盤式離心光式沉澱測定儀(Disc Centrifuge Photosedimentometer)(DCP)尺寸分析器(Brookhaven Instruments Corporation)測量下列描述的顏料之顆粒尺寸分佈及提供在表3中。
DCP測量程序：DCP測量程序：首先經由研碎呈1：2比率(顏料：分散劑)的顏料乾粉與分散劑Nuosperse W-28來製備用於DCP分析之操作分散液。然後，使用超音波浴接著超音波喇叭，以1：100之比率將所產生的糊狀物分散在去離子水中。在Brookhaven
BI-DCP顆粒尺寸分析器上，於室溫下，使用盤速度10,000rpm進行測量。使用Brookhaven BI-DCP軟體版本5.87用於資料處理及顆粒尺寸計算。
實施例1：氯化酞青銅(m=0.71；n=0.29)之製備
在1升樹脂燒瓶中，將92.8克酞酸酐、27.2克3-氯酞酸酐、11.0克4-氯酞酸酐、163.5克尿素、20.7克氯化銅(I)、0.5克二鉬酸銨及705克二氯甲苯加熱至200℃伴隨著攪動。允許在200℃下攪拌該反應2小時。在此時間後，將該等成分冷卻至室溫及在真空下移除溶劑。允許在90℃下，於2500克水及100克濃硫酸中攪拌該粗產物殘餘物2小時。藉由過濾分離該粗產物壓濾餅，清洗至導電度少於100微姆歐/公分，乾燥，然後在Osterizer混合器中均質化。已藉由X射線分析(表1，圖1)證實所獲得的藍色粗產物(粗產物#1)。然後，在實驗室揉捏器中，使用鹽(216克)及丙二醇(53克)於80℃下鹽磨粗產物#1(27克)6小時。在鹽磨完成時，將該混合物懸浮在水中，於周溫下攪拌，及加入濃HCl直到該料漿具有pH<1.0。然後，將該料漿加熱至90℃，保持1小時，然後過濾。藉由過濾分離出該顏料，清洗至導電度少於
100微姆歐/公分，乾燥，在Osterizer混合器中均質化及通過60目篩，以獲得成品(顏料#1)。在Skandex搖動器上，使用8.83/3.19的顏料/結合劑，將顏料#1及標準物(Palomar®Blue 248-4816)分散在DuPont水載型塗料系統中3小時。在溫度控制及溼氣控制的噴灑台中，將包括顏料#1及標準物的塗料調配物噴灑在面板上。在該噴灑台內的設備稱為自動測試面板噴灑機器(Spraymation，Inc.)。
表4顯示出該面板在50鋁(DuPont 50%鋁水載型塗料系統[在塗料膜中的鋁/顏料比率係50/50，從產品碼：54-47166及顏料調配])中的CIE L*a*b*資料。使用X-Rite MA-68多角度分光光度計獲得該50鋁之資料。在表3中的資料顯示出顏料#1在色澤及明度上接近標準物、具有比標準物好的色度及具有基本上中性的色彩傳播，如由傳播(ΔH=0.3)指示出。用語”色彩傳播”指為一金屬塗料膜當從視角15°至110°測量時的表觀色值之變化。於本文中使用的用語”傳播Δ色澤(傳播ΔH)”指為在15°測量與110°測量間之色澤差異。當在二種測量間無差異時(即，傳播ΔH=0)，該向下傳播(down travel)係說明為”中性”。該傳播ΔH愈小，該塗料的外觀愈好。在表3中的資料證實本發明的單氯化酞青銅顏料可係可商業購得的四氯酞青銅顏料之替代物，及從安全性、毒性及環境視角來看更優良。
表4：顏料#1相對於標準物在50鋁中的CIE L*a*b*資料(ΔH、ΔC、ΔL及ΔE未調整至相等強度)
實施例2：氯化酞青銅(m=0.60；n=0.40)之製備
在1升樹脂燒瓶中，將92.8克酞酸酐、22.6克3-氯酞酸酐、15.5克4-氯酞酸酐、163.5克尿素、20.7克氯化銅(I)、0.5克二鉬酸銨及705克二氯甲苯加熱至200℃伴隨著攪動。允許在200℃下攪拌該反應2小時。在此時間之後，將該反應混合物冷卻至室溫及在真空下移除溶劑。允許在90℃下，於2800克水及100克濃硫酸中攪拌該殘餘物2小時。藉由過濾分離出顏料，清洗至導電度少於100微姆歐/公分，乾燥，然後在Osterizer混合器中均質化。已藉由X射線分析(表2，圖2)證實所獲得的藍色粗產物(粗產物#2)。在周溫下，於不銹鋼罈
中球磨粗產物#2(37.5克)6小時。該罈包括~870克¼英吋球及~97克小釘子。然後，在實驗室揉捏器中，使用鹽(248克)及丙二醇(61克)，於80℃下鹽磨該經球磨的粗產物(31克)6小時。在鹽磨完成時，該混合物係懸浮在水中，於周溫下攪拌，及加入濃HCl直到該料漿具有pH<1.0。然後，將該料漿加熱至90℃，保持1小時，然後過濾。藉由過濾分離出顏料，清洗至導電度少於100微姆歐/公分，乾燥，在Osterizer混合器中均質化及通過60目篩以獲得成品(顏料#2)。在Skandex搖動器上，使用8.83/3.19的顏料/結合劑，將顏料#2及標準物(Palomar®Blue 248-4816)分散在DuPont水載型塗料系統中3小時。在溫度控制及溼氣控制的噴灑台中，將包括顏料#2及標準物的塗料調配物噴灑在面板上。在該噴灑台內的設備稱為自動測試面板噴灑機器(Spraymation，Inc.)。
表6顯示出該面板在50鋁(DuPont 50%鋁水載型塗料系統[在塗料膜中的鋁/顏料比率係50/50，從產品碼：54-47166及顏料調配])中的CIE L*a*b*資料。使用X-Rite MA-68多角度分光光度計獲得該50鋁的資料。在表4中的資料顯示出顏料#2具有色度類似於標準物及具有基本上中性色彩傳播，如由該傳播(ΔH=-0.9)指示出。此資料證實本發明的單氯化酞青銅顏料可係可商業購得的四氯酞青銅顏料之替代物，及從安全性、毒性及環境視角來看更優良。
下列實施例描述出此技術的組成物之製備及使用。藉由X射線繞射(Siemens D5000繞射儀)分析根據這些實施例製備的顏料。
實施例3：氯化酞青銅(m=0.71；n=0.29)(PMV-00156-121/PMV-00156-125)之製備
在1升樹脂燒瓶中，將92.8克酞酸酐、27.2克3-氯酞酸酐、11.0克4-氯酞酸酐、163.5克尿素、10.4克氯化銅(I)、16.7克硫酸銅(II)、0.5克二鉬酸銨及485克輕分枝的烷基苯溶劑加熱至200℃伴隨著攪動。允許在200℃下攪拌該反應2.5-3小時。在此時間之後，將該成
分冷卻至室溫及在真空下移除溶劑。允許在90℃下，於2500克水及100克濃硫酸中攪拌該粗產物殘餘物2小時。藉由過濾分離出該粗產物壓濾餅，清洗至導電度少於100微姆歐/公分，乾燥，然後在Osterizer混合器中均質化。已藉由X射線分析證實所獲得的藍色粗產物(粗產物#3)。然後，在實驗室揉捏器中，使用鹽(216克)及丙二醇(52克)，於80℃下鹽磨粗產物#3(27克)6小時。在鹽磨完成時，該混合物係懸浮在水中，在周溫下攪拌，及加入濃HCl直到該料漿具有pH<1.0。然後，將該料漿加熱至90℃，保持1小時，然後過濾。藉由過濾分離出顏料，清洗至導電度少於100微姆歐/公分，乾燥，在Osterizer混合器中均質化及通過60目篩以獲得成品。在Skandex搖動器上，使用8.83/3.19之顏料/結合劑，將顏料#3及標準物(Palomar®Blue 248-4816)分散在DuPont水載型塗料系統中3小時。在溫度控制及溼氣控制的噴灑台中，將該包括顏料#3及標準物的塗料調配物噴灑在面板上。在該噴灑台內的設備稱為自動測試面板噴灑機器(Spraymation，Inc.)。
表8顯示出該面板在50鋁(DuPont 50%鋁水載型塗料系統[在塗料膜中的鋁/顏料比率為50/50，從產品碼：54-47166及顏料調配])中的CIE L*a*b*資料。使用X-Rite MA-68多角度分光光度計獲得該50鋁的資料。在表5中之資料顯示出顏料#3具有色度類似於標準物及具有基本上中性色彩傳播，如由該傳播(ΔH=1.1)指示出。此資料證實本發明的單氯化酞青銅顏料可係可商
業購得的四氯酞青銅顏料之替代物，及從安全性、毒性及環境視角來看更優良。
Claims (10)
- 一種氯化酞青銅顏料組成物，其包含多於50%的β結晶形式，其具有下列結構：其具有α及β位置，其中在酞青上的α及β位置之氯取代基係由下列定義：0.4<m+n
4 m
n n>0.2其中m代表在α位置處之平均氯取代基數目，及n代表在β位置處之平均氯取代基數目。
- 如請求項1之酞青顏料組成物，其具有顆粒尺寸在約20-90奈米間。
- 如請求項1之酞青顏料組成物，其具有顆粒尺寸在約30-70奈米間。
- 如請求項1之酞青顏料組成物，其在95W色調(tint)中具有色澤(hue)角度(H)在約225-242°間。
- 如請求項1之酞青顏料組成物，其中該顏料組成物包含至少一種添加劑。
- 如請求項5之酞青顏料組成物，其中該添加劑係一種顏料衍生物。
- 如請求項6之酞青顏料組成物，其中該添加劑係一種經修改的酞青顏料衍生物。
- 如請求項7之酞青顏料組成物，其中該添加劑係一種磺酸化的酞青顏料衍生物。
- 如請求項1之酞青顏料組成物，其中該顏料組成物係使用在汽車用塗料系統中。
- 一種塗佈物、油墨、水載型或溶劑型顏料製劑、電子照像色劑及顯色劑、塑膠、濾色片、或粉末塗佈材料，其包含如請求項1之氯化酞青銅顏料組成物。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080035026A1 (en) * | 2006-08-09 | 2008-02-14 | Sun Chemical Corporation | Phthalocyanine pigments with neutral metallic down flop |
Family Cites Families (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2910482A (en) * | 1955-02-08 | 1959-10-27 | Du Pont | Phthalocyanine coloring matters in pigmentary form |
| GB925379A (en) | 1962-01-05 | 1963-05-08 | Geigy Co Ltd | Process for the halogenation of phthalocyanines |
| US3300512A (en) | 1964-09-04 | 1967-01-24 | Allied Chem | Synthesis of metal-containing phthalocyanines |
| US3392830A (en) | 1965-06-29 | 1968-07-16 | Ibm | Electrical component tester with test multiplexing |
| DE1569618A1 (de) | 1966-06-23 | 1970-05-27 | Allied Chem | Verfahren zur Herstellung von halogenierten Phthalocyaninen |
| US3770765A (en) * | 1971-11-11 | 1973-11-06 | Du Pont | Production of chlorine-containing copper phthalocyanines |
| US3772048A (en) * | 1972-06-14 | 1973-11-13 | Chemetron Corp | Method for reducing oil absorption of pigment containing beta-copper phthalocyanine and composite green pigment |
| AU497471B2 (en) | 1975-09-01 | 1978-12-14 | Imp; 7 Chemical Industries Limited | Phthalocyanines |
| JPS62158284A (ja) | 1986-01-07 | 1987-07-14 | Asahi Chem Ind Co Ltd | アルミクロロフタロシアニンの製造法 |
| JPH0794611B2 (ja) | 1988-01-29 | 1995-10-11 | 東洋インキ製造株式会社 | ハロゲン化銅フタロシアニンの製造方法 |
| US5282896A (en) * | 1989-05-19 | 1994-02-01 | Toyo Ink Manufacturing Co., Ltd. | Process for producing phthalocyanine pigment composition containing highly halogenated different-metalo-phthalocyanine |
| GB9007924D0 (en) * | 1990-04-07 | 1990-06-06 | Ciba Geigy Ag | Production of pigments |
| JP3077458B2 (ja) | 1993-07-23 | 2000-08-14 | 東洋インキ製造株式会社 | アルミニウムフタロシアニン組成物の製造法 |
| GB9517565D0 (en) * | 1995-08-26 | 1995-10-25 | Ciba Geigy Ag | Pigment compositions |
| JPH09291223A (ja) * | 1996-04-26 | 1997-11-11 | Toyo Ink Mfg Co Ltd | β型銅フタロシアニン顔料の製造方法 |
| DE19745922A1 (de) * | 1997-10-17 | 1999-04-22 | Basf Ag | Verfahren zur Überführung von halogenierten Kupferphtalocyanin-Rohpigmenten in eine für die Anwendung geeignete Pigmentform |
| RU2164233C1 (ru) | 1999-09-17 | 2001-03-20 | Государственный научный центр Российской Федерации "НИОПИК" | Способ получения фталоцианина хлоралюминия |
| US6379450B1 (en) * | 2000-03-08 | 2002-04-30 | Sun Chemical Corporation | Process for producing β-phase copper phthalocyanine pigment |
| JP2001270885A (ja) | 2000-03-27 | 2001-10-02 | Toyo Ink Mfg Co Ltd | アルミニウムフタロシアニン類の製造方法 |
| JP4407097B2 (ja) | 2001-02-23 | 2010-02-03 | Ｄｉｃ株式会社 | カラーフィルター |
| CN1285926C (zh) | 2001-02-23 | 2006-11-22 | 大日本油墨化学工业株式会社 | 滤色片 |
| JP2003176424A (ja) | 2001-12-12 | 2003-06-24 | Dainippon Ink & Chem Inc | 緑色着色剤組成物及びカラーフィルター |
| JP2003176423A (ja) | 2001-12-12 | 2003-06-24 | Dainippon Ink & Chem Inc | 緑色着色剤組成物及びカラーフィルター |
| JP2005002250A (ja) * | 2003-06-13 | 2005-01-06 | Toyo Ink Mfg Co Ltd | β型銅フタロシアニン顔料の製造方法 |
| US7255733B2 (en) * | 2003-06-20 | 2007-08-14 | Toyo Ink Mfg. Co., Ltd. | Process for the production of β type copper phthalocyanine pigment and a use thereof |
| JP2013079399A (ja) * | 2006-07-25 | 2013-05-02 | Dainichiseika Color & Chem Mfg Co Ltd | 微細化顔料の製造方法および顔料着色剤 |
| DE102007033191A1 (de) | 2007-07-17 | 2009-01-22 | Clariant International Ltd. | Feinteilige epsilon-Kupferphthalocyanin-Pigmentzubereitung |
| DE102008026584A1 (de) | 2008-06-03 | 2009-12-10 | Clariant International Limited | Verbessertes Cyanfarbmittel |
| JP5481873B2 (ja) * | 2009-02-18 | 2014-04-23 | 東洋インキＳｃホールディングス株式会社 | β型フタロシアニン顔料およびそれを用いた着色組成物 |
| JP5229819B2 (ja) | 2009-04-01 | 2013-07-03 | 株式会社レヨーン工業 | 除塵装置 |
| CN101717401B (zh) | 2009-11-18 | 2012-01-11 | 淄博福颜化工集团有限公司 | 一种氯铝酞菁的制法 |
| GB201004416D0 (en) * | 2010-03-17 | 2010-05-05 | Fujifilm Imaging Colorants Ltd | Phthalocyanines and their use in ink-jet printing |
| JP5866955B2 (ja) * | 2011-10-17 | 2016-02-24 | 住友化学株式会社 | 着色硬化性樹脂組成物 |
| CN102516813B (zh) * | 2011-12-26 | 2013-06-19 | 上海捷虹颜料化工集团股份有限公司 | 一种绿色有机颜料组合物的制备方法 |
| JP6418441B2 (ja) * | 2014-07-18 | 2018-11-07 | Dic株式会社 | 塩素化銅フタロシアニン顔料および着色組成物 |
| JP6662912B2 (ja) * | 2015-06-04 | 2020-03-11 | サン ケミカル コーポレイション | 塩素化銅フタロシアニン顔料 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080035026A1 (en) * | 2006-08-09 | 2008-02-14 | Sun Chemical Corporation | Phthalocyanine pigments with neutral metallic down flop |
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| WO2016196715A1 (en) | 2016-12-08 |
| JP2018522966A (ja) | 2018-08-16 |
| EP3303480B1 (en) | 2022-03-09 |
| KR102007600B1 (ko) | 2019-08-05 |
| JP6662912B2 (ja) | 2020-03-11 |
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| US11059978B2 (en) | 2021-07-13 |
| CN111777870B (zh) | 2022-06-07 |
| EP3303480A1 (en) | 2018-04-11 |
| JP2020073702A (ja) | 2020-05-14 |
| KR102360691B1 (ko) | 2022-02-08 |
| JP6978531B2 (ja) | 2021-12-08 |
| CN111777870A (zh) | 2020-10-16 |
| US20180215921A1 (en) | 2018-08-02 |
| KR20190091570A (ko) | 2019-08-06 |
| KR20180012305A (ko) | 2018-02-05 |
| TW201708414A (zh) | 2017-03-01 |
| CN107922750A (zh) | 2018-04-17 |
| CN107922750B (zh) | 2020-07-10 |
| US20200109291A1 (en) | 2020-04-09 |
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