CN101817992A - Preparation process of epsilon-crystal form copper phthalocyanine - Google Patents
Preparation process of epsilon-crystal form copper phthalocyanine Download PDFInfo
- Publication number
- CN101817992A CN101817992A CN201010148776A CN201010148776A CN101817992A CN 101817992 A CN101817992 A CN 101817992A CN 201010148776 A CN201010148776 A CN 201010148776A CN 201010148776 A CN201010148776 A CN 201010148776A CN 101817992 A CN101817992 A CN 101817992A
- Authority
- CN
- China
- Prior art keywords
- copper phthalocyanine
- epsilon
- crystal form
- crystal
- form copper
- 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.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 138
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [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 claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 21
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].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 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000004898 kneading Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 24
- 238000005516 engineering process Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 230000001404 mediated effect Effects 0.000 claims description 8
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 3
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 abstract 1
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 abstract 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010306 acid treatment Methods 0.000 abstract 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract 1
- 235000013877 carbamide Nutrition 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000005755 formation reaction Methods 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 210000003298 dental enamel Anatomy 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 150000004996 alkyl benzenes Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- QRPPSTNABSMSCS-UHFFFAOYSA-N 4-tert-butyl-1,2-dimethylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1C QRPPSTNABSMSCS-UHFFFAOYSA-N 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- -1 polyoxyethylene Polymers 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group 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 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229940045136 urea Drugs 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CUIFMTWQFFCFCH-UHFFFAOYSA-N 2-ethylhexylbenzene Chemical compound CCCCC(CC)CC1=CC=CC=C1 CUIFMTWQFFCFCH-UHFFFAOYSA-N 0.000 description 1
- HSZAFGSRDPBOLC-UHFFFAOYSA-N ClC(CO)O.[Na] Chemical compound ClC(CO)O.[Na] HSZAFGSRDPBOLC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000002520 cambial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention belongs to the technical field of copper phthalocyanine, and discloses a preparation process of epsilon-crystal form copper phthalocyanine which is also called C.I. pigment blue 15:6.The invention has a main technical scheme comprising the following steps: adopting phthalic anhydride, chlorophthalic anhydride, carbamide and copper chloride to synthesize monochloro copper phthalocyanine in the presence of a specific catalyst; carrying out acid treatment on the monochloro copper phthalocyanine to prepare an alpha-crystal form copper phthalocyanine intermediate product; and adding copper phthalocyanine derivates and a small amount of the epsilon-crystal form copper phthalocyanine of a known crystal form as seed crystals, and kneading with a high shear force in an organic solvent DEG to prepare the epsilon-crystal form copper phthalocyanine (C.I. pigment blue 15:6) which has fine heat resistance and weather resistance and pure and bright strong royal blue tone.
Description
Technical field
The present invention relates to a kind of technology of preparing of pigment dyestuff new crystal, especially ε-epsilon-crystal form copper phthalocyanine (or C.I. pigment Blue 15: preparation technology 6).
Background technology
Copper phthalocyanine is known crystal formation more than five kinds, is referred to as α-crystal formation, beta-crystal, γ-crystal formation, δ-crystal formation and ε-epsilon-crystal form copper phthalocyanine, claims the copper phthalocyanine of R-crystal formation to come down to be equal to ε-crystal formation in the patent.Various different crystal forms copper phthalocyanines, show different physical property and color characteristics, such as: α-epsilon-crystal form copper phthalocyanine provides the ruddiness blue cast in low-melting ink vehicle, comprise astable α-crystal formation (C.I. pigment Blue 15) and stable alpha-crystal formation (C.I. pigment Blue 15: 1); The beta-crystal copper phthalocyanine provides the greenish blue tone, comprises anti-crystalline beta-crystal (C.I. pigment Blue 15: 3) with beta-crystal (the C.I. pigment Blue 15: 4) of the brilliant deflocculate of resistive connection; γ-epsilon-crystal form copper phthalocyanine, δ-epsilon-crystal form copper phthalocyanine provide the tone between α-epsilon-crystal form copper phthalocyanine, beta-crystal copper phthalocyanine.(the C.I. pigment Blue 15: 6) be the strongest crystal formation of ruddiness, it has excellent solvent resistance and heat-resistant stability than the more purified ruddiness blue cast of α-epsilon-crystal form copper phthalocyanine, γ-epsilon-crystal form copper phthalocyanine or δ-epsilon-crystal form copper phthalocyanine to ε-epsilon-crystal form copper phthalocyanine.
(the C.I. pigment Blue 15: 6) Technology mainly contains two types from existing patent report: a kind of technology is to be basic raw material with the phthalic nitrile to preparation ε-epsilon-crystal form copper phthalocyanine, and cost is higher; Another kind of technology then is that Tetra hydro Phthalic anhydride-urea is raw material, has that the technology cost is low, the yield advantages of higher.
Japan Toyo Ink company delivers patent (Japan Kokai 73-76925), by phthalic nitrile, cuprous chloride, urea and ammonium molybdate, in the oil of mirbane solvent, provide low chloro copper phthalocyanine, low chloro copper phthalocyanine 11g and 39g copper phthalocyanine be dissolved in 500 part 98% the sulfuric acid, precipitation, filtration, washing, drying in the water are with 100 parts in sodium-chlor, 25 parts of polyoxyethylene glycol, mediated 10 hours at 100-140 ℃, provide ε-epsilon-crystal form copper phthalocyanine. be to adopt to mediate in the polyethylene glycol medium to handle.
(Japan Kokai 73-59136) also reported employing copper phthalocyanine and its derivative in the Toyo Ink patent, (CuPc)-and CO-CH
2-NHC
2H
5, under strong shear action and sodium-chlor, ethylene glycol, grind at 80-160 ℃ and to mediate 10 hours, washing, drying provide ε-epsilon-crystal form copper phthalocyanine.
Big (the clear 57-141453 of Japanese ink house journal, 1982), in alkyl benzene solvent, interact, in the process of synthesizing copper phthalocyanine with the thing that organises, urea, the mantoquita that forms the phthalocyanine ring, add phthalocyanine derivates and a small amount of ε-epsilon-crystal form copper phthalocyanine, synthetic ε-epsilon-crystal form copper phthalocyanine.For example:
In potheater, add 120 parts of phthalimides, 104 parts of urea, 20.3 parts of cuprous chlorides, 0.8 part of ammonium molybdate, 300 parts of 2-ethylhexyl benzene, stir ε-epsilon-crystal form copper phthalocyanine and 12 parts of copper phthalocyanine derivative things with following structure of adding 12 parts down:
Big Japanese ink company delivers the patent (clear 57-149358,1982) of the similar content of another piece, is reported in synthetic ε-epsilon-crystal form copper phthalocyanine in the alkyl benzene solvent.
In potheater, add phthalimide, part urea, cuprous chloride, ammonium molybdate, benzene derivative, stir the copper phthalocyanine derivative thing that adds ε-epsilon-crystal form copper phthalocyanine and following structure down:
SUMITOMO CHEMICAL chemical company delivers patent (clear 64-1766,1989), at the organic solvent tetramethylene sulfone, with Tetra hydro Phthalic anhydride, urea, cuprous chloride, adds the copper phthalocyanine sulfonic acid of different sulfonation degree in reaction, directly synthetic ε-epsilon-crystal form copper phthalocyanine product.
In addition, also report prepared ε-epsilon-crystal form copper phthalocyanine of implementing the crystal conversion processing by some astable type copper phthalocyanine.For example: adopt δ-epsilon-crystal form copper phthalocyanine through grinding in German BASF (BASF) house journal (DE 2,210,072,1972), reflow treatment in butanone-2 prepares ε-epsilon-crystal form copper phthalocyanine product again.
BASF AG delivers patent (BP 1,411,880,1973), and report adopts instability mode crystal formations such as α-crystal formation, γ-crystal formation, δ-epsilon-crystal form copper phthalocyanine, prepares ε-epsilon-crystal form copper phthalocyanine product with the method for solvent treatment; The astable crystal formation that is adopted is with in the beta-crystal copper phthalocyanine vitriolization, the copper phthalocyanine vitriol hydrolysis that generates, obtain different astable epsilon-crystal form copper phthalocyanine products, when the dispersing apparatus with high shear force carries out ball milling, to there be a certain proportion of ε-epsilon-crystal form copper phthalocyanine to produce, wherein from the easiest formation of γ-epsilon-crystal form copper phthalocyanine ε-epsilon-crystal form copper phthalocyanine, so γ-epsilon-crystal form copper phthalocyanine is best suited at industrial preparation ε-epsilon-crystal form copper phthalocyanine; When ball milling, form α-crystal formation/ε-crystal formation mix products simultaneously usually, select specific solvent treatment again, finally all change ε-epsilon-crystal form copper phthalocyanine into.
Comprehensive above-mentioned existing Technology, no matter by direct synthetic method, or the method for crystal formation conversion, all there is some deficiency in final ε-epsilon-crystal form copper phthalocyanine product at application performance.Unsettled α-epsilon-crystal form copper phthalocyanine, in the crystal conversion course of processing as: adopt solvent treatment, ball-milling processing, when kneading is handled, be transformed into the copper phthalocyanine while of ε-crystal formation by α-epsilon-crystal form copper phthalocyanine, have a small amount of α-epsilon-crystal form copper phthalocyanine and be transformed into the beta-crystal copper phthalocyanine, thereby cause copper phthalocyanine product purity of color, tinctorial strength, solvent resistance, the heat-resistant stability of ε-crystal formation can all have certain deficiency.Copper phthalocyanine product technical indicator by detecting existing ε-crystal formation is as follows: contrast gradient is lower than 1440; Purity of color (saturation ratio) Δ C (detects with color measurement instrument) between 0.200-0.312; Glossiness is up to 38 (detecting with glossometer); Tinctorial strength and standard are than 100%; Solvent resistance (refluxing xylene) 98% heat-resistingly is not higher than 300 ℃.
In addition, development along with society, liquid-crystal display is developed to big liquid crystal panel aspect by original little liquid crystal panel, therefore requires purity of color, glossiness, the contrast gradient of used pigment further to improve, and the product of existing Technology can not satisfy the needs of development.
A kind of phthalocyanine blue 15:6 pigment prepared technology was once disclosed although number of patent application is 200610012573.1 application for a patent for invention.But, can not prepare stable phthalocyanine blue 15:6 pigment according to the record of this patent application specification.
Summary of the invention
Purpose of the present invention just provides a kind of ε-epsilon-crystal form copper phthalocyanine (C.I. pigment Blue 15: preparation technology 6) that heat-resisting, weather-proof good, strong ruddiness blue cast that color is pure, bright-coloured is arranged.
Realize that the technical scheme that above-mentioned purpose of the present invention adopted is:
The technology of preparation ε-epsilon-crystal form copper phthalocyanine comprises:
By Tetra hydro Phthalic anhydride, chlorophthalic acid (acid anhydride), urea, cuprous chloride, synthesis of alpha-single chloro copper phthalocyanine in the presence of catalyzer;
Prepare intermediate product α-epsilon-crystal form copper phthalocyanine with vitriolization;
The kneading that utilizes kneader to carry out crystal conversion is handled;
Acid is boiled, soda boiling is handled, and filters washing, drying; Isolate pure ε-epsilon-crystal form copper phthalocyanine (C.I. pigment Blue 15: 6) product.
In addition: describedly prepare the intermediate product monochloro in the copper phthalocyanine intermediate product operation with vitriolization, vitriolic concentration is 50-98%; In the kneading treatment process of described crystal conversion, in the DEG solvent, add sodium-chlor, adopt 4000 liter kneaders of high shear force, mediated 5-10 hour; Slit design between the ∑ of described kneader-shape mixing page sheet and the kneader wall is between the 0.1-0.3 millimeter; The described utilization in the kneading treatment process that kneader carries out crystal conversion, adopting the consumption of pigment dyestuff derivative is the 5-30% of parent pigment; The described utilization in the kneading treatment process that kneader carries out crystal conversion, the ε-epsilon-crystal form copper phthalocyanine that adds known crystal formation is as crystal seed, and amount of seed is the 5-15% of parent pigment.
The inventive method is in mediating treating processes, and the derivative that adds copper phthalocyanine can improve the brilliant and deflocculate stability of resistive connection of product. and the derivative that adds copper phthalocyanine can be enumerated following type:
Such as: the low chlorinated derivatives (I) of copper phthalocyanine, copper phthalocyanine methylolation and phthalic imidine condensation product (II), the quaternary ammonium salt derivative (III) that copper phthalocyanine sulfonic acid and octadecyl dimethyl amine (fat tertiary amine) effect generate, copper phthalocyanine SULPHURYL CHLORIDE and N, the copper phthalocyanine sulphonamide products (IV) that the effect of N-diethyl propyldiamine generates etc., its substituent numerical value n can from 0.1 to 2 wait:
(derivative I) (derivative I I)
(derivative III) (derivative I V)
Adopt specific kneader equipment in the inventive method,, must adopt high-intensity material manufacturing, have different special construction designs with the kneader of routine for guaranteeing in the desired high shearing force of crystal conversion; Wherein the gap size between the ∑ of kneader-shape mixing page sheet and the kneader wall is one of important factor in order of crystal conversion.
Description of drawings
Fig. 1 is intermediate product α-epsilon-crystal form copper phthalocyanine X-ray powder diffraction curve;
Fig. 2 is the ε-epsilon-crystal form copper phthalocyanine X-ray powder diffraction curve of prepared of the present invention;
Fig. 3 is known ε-epsilon-crystal form copper phthalocyanine (commodity) X-ray powder diffraction curve.
Embodiment
Be described in further details below in conjunction with the structure of accompanying drawing a kind of IC engine cleaner filter paper provided by the invention.
Alkyl benzene solvent (Japanese AS-P2) is joined in the enamel still for 1500 kilograms, add 500 kilograms of Tetra hydro Phthalic anhydrides then, 300 kilograms of chlorophthalic acids (acid anhydride), 1600 kilograms in urea, 210 kilograms of cuprous chlorides, 16 kilograms of ammonium molybdates, be warming up to 220 ℃, the pressure-controlling in the enamel still is at 3.5 kilograms/cm
2, under 220 ± 5 ℃ condition, be incubated 5 hours, promptly get and hang down (85%) 850 kilogram of chloro copper phthalocyanine crude product.
With concentration is that 50% sulfuric acid joins in second enamel still for 870 liters, be cooled to 30 ℃, drop into (85%) 200 kilogram of above-mentioned obtained low chloro copper phthalocyanine crude product then, open and stir molten 6 hours of acid, put in the thinning tank, be warming up to 100 ℃, be incubated 8 hours, filter, spraying drying is also carried out in washing under 70 ℃ temperature, purity is 165 kilograms of 98% intermediate products.
Get 400 kilograms intermediate product, 2400 kilograms salt and 260 kilograms DEG and make solvent, add 35 kilograms copper phthalocyanine derivative thing (derivative I V), 20 kilograms C.I. pigment Blue 15: 6 do crystal seed, put in 4000 liters the kneader and mediated 8 hours, 100 liters of desalination after vulcanization acid, acid was boiled 10 hours, add 200 kilograms of caustic soda, soda boiling 6 hours, after filtration, washing, drying, the copper phthalocyanine product of ε-crystal formation.
Alkyl benzene solvent (Japanese AS-P2) is joined in the enamel still for 1500 kilograms, add 800 kilograms of Tetra hydro Phthalic anhydrides then, 200 kilograms of chlorophthalic acids (acid anhydride), 2000 kilograms in urea, 250 kilograms of cuprous chlorides, 15 kilograms of molybdic acids, be warming up to 210 ℃, the pressure-controlling in the enamel still is at 3.5 kilograms/cm
2, under 210 ± 5 ℃ condition, be incubated 8 hours, promptly get and hang down (85%) 1082 kilogram of chloro copper phthalocyanine crude product.
With concentration is that 60% sulfuric acid joins in second enamel still for 850 liters, be cooled to 30 ℃, drop into (85%) 200 kilogram of above-mentioned obtained low chloro copper phthalocyanine crude product then, open and stir molten 7 hours of acid, put in the thinning tank, be warming up to 100 ℃, be incubated 7 hours, filter, spraying drying is also carried out in washing under 85 ℃ temperature, purity is 160 kilograms of 99% intermediate products.
Get 400 kilograms intermediate product, 2350 kilograms salt and 260 kilograms DEG and make solvent, add 30 kilograms copper phthalocyanine derivative thing (derivative III), 25 kilograms C.I. pigment Blue 15: 6 do crystal seed, put in 4000 liters the kneader and mediated 9 hours, 100 liters of desalination after vulcanization acid, acid was boiled 9 hours, add 200 kilograms of caustic soda, soda boiling 7 hours, after filtration, washing, drying, the copper phthalocyanine product of ε-crystal formation.
Embodiment 3
Alkyl benzene solvent (Japanese AS-P2) is joined in the enamel still for 1500 kilograms, add 700 kilograms of Tetra hydro Phthalic anhydrides then, 400 kilograms of chlorophthalic acids (acid anhydride), 1800 kilograms in urea, 230 kilograms of cuprous chlorides, 18 kilograms of ammonium molybdates, be warming up to 210 ℃, the pressure-controlling in the enamel still is at 3.5 kilograms/cm
2, under 210 ± 5 ℃ condition, be incubated 7 hours, promptly get (85%) 1200 kilogram of the low copper phthalocyanine crude product of monochloro.
With concentration is that 70% sulfuric acid joins in second enamel still for 820 liters, be cooled to 30 ℃, drop into (85%) 200 kilogram of above-mentioned obtained low chloro copper phthalocyanine crude product then, open and stir molten 5 hours of acid, put in the thinning tank, be warming up to 100 ℃, be incubated 7.5 hours, filter, washing, and under 75 ℃ temperature, carry out spraying drying, purity is 170 kilograms of 97% intermediate products.
Get 400 kilograms intermediate product, 2200 kilograms salt and 260 kilograms DEG and make solvent, add 25 kilograms copper phthalocyanine derivative thing (derivative I I), 30 kilograms C.I. pigment Blue 15: 6 do crystal seed, put in 4000 liters the kneader and mediated 10 hours, 100 liters of desalination after vulcanization acid, acid was boiled 10 hours, add 200 kilograms of caustic soda, soda boiling 5 hours, after filtration, washing, drying, the copper phthalocyanine product of ε-crystal formation.
Alkyl benzene solvent (Japanese AS-P2) is joined in the enamel still for 1500 kilograms, add 600 kilograms of Tetra hydro Phthalic anhydrides then, 100 kilograms of chlorophthalic acids (acid anhydride), 1700 kilograms in urea, 210 kilograms of cuprous chlorides, 16 kilograms of phospho-molybdic acids, be warming up to 230 ℃, the pressure-controlling in the enamel still is at 3.5 kilograms/cm
2, under 230 ± 5 ℃ condition, be incubated 6 hours, promptly get and hang down (85%) 807 kilogram of chloro copper phthalocyanine crude product.
With concentration is that 80% sulfuric acid joins in second enamel still for 830 liters, be cooled to 30 ℃, drop into (85%) 200 kilogram of the low copper phthalocyanine crude product of above-mentioned obtained monochloro then, open and stir molten 7.5 hours of acid, put in the thinning tank, be warming up to 100 ℃, be incubated 6.5 hours, filter washing and also under 80 ℃ temperature, carry out spraying drying, purity is 175 kilograms of 98% intermediate products.
Get 400 kilograms intermediate product, 2450 kilograms salt and 260 kilograms DEG and make solvent, add 25 kilograms copper phthalocyanine derivative thing (derivative III), 15 kilograms C.I. pigment Blue 15: 6 do crystal seed, put in 4000 liters the kneader and mediated 5 hours, 100 liters of desalination after vulcanization acid, acid was boiled 5 hours, add 200 kilograms of caustic soda, soda boiling 6 hours, after filtration, washing, drying, the copper phthalocyanine product of ε-crystal formation.
Embodiment 5
Alkyl benzene solvent (Japanese AS-P2) is joined in the enamel still for 1500 kilograms, add 750 kilograms of Tetra hydro Phthalic anhydrides then, 500 kilograms of chlorophthalic acids (acid anhydride), 1900 kilograms in urea, 240 kilograms of cuprous chlorides, 15 kilograms of Sodium orthomolybdates, be warming up to 230 ℃, the pressure-controlling in the enamel still is at 3.5 kilograms/cm
2, under 230 ± 5 ℃ condition, be incubated 7 hours, promptly get and hang down (85%) 1050 kilogram of chloro copper phthalocyanine crude product.
With concentration is that 55% sulfuric acid joins in second enamel still for 870 liters, be cooled to 30 ℃, drop into (85%) 200 kilogram of the low copper phthalocyanine crude product of above-mentioned obtained monochloro then, open and stir molten 5.5 hours of acid, put in the thinning tank, be warming up to 100 ℃, be incubated 7 hours, filter washing and also under 75 ℃ temperature, carry out spraying drying, purity is 165 kilograms of 99% intermediate products.
Get 400 kilograms intermediate product, 2300 kilograms salt and 260 kilograms DEG and make solvent, add 30 kilograms copper phthalocyanine derivative thing (derivative I), 20 kilograms C.I. pigment Blue 15: 6 do crystal seed, put in 4000 liters the kneader and mediated 8 hours, 100 liters of desalination after vulcanization acid, acid was boiled 8 hours, added 200 kilograms of caustic soda, soda boiling 7 hours, be washed to drying after filtration, get the copper phthalocyanine product of ε-crystal formation.
In the above-described embodiments, in order to improve the kneading crystal conversion effect of kneader, improve its shearing force, wherein the slit design between the ∑ of kneader-shape mixing page sheet and the kneader wall is between the 0.1-0.3 millimeter.
ε-epsilon-crystal form copper phthalocyanine according to the inventive method preparation than the product of the prepared of introducing in the previous patent, has purer more bright-coloured ruddiness blue color, higher tinctorial strength, more excellent solvent-resistance can with the heat-resistant stability energy:
---detect by the copper phthalocyanine to the prepared ε-crystal formation that goes out of above five embodiment, the copper phthalocyanine of these ε-crystal formations has purer more bright-coloured ruddiness blue color; Contrast gradient is 1700-1800 (standard 〉=1440); Purity of color (saturation ratio) Δ C=0-0.022 (detecting) with color measurement instrument; Glossiness is 40-45 (detecting with glossometer); Tinctorial strength and standard ratio can be between 100-105%; Solvent resistance (refluxing xylene) has all reached 102%, heat-resisting being stabilized between 310-315 ℃.
α-the epsilon-crystal form copper phthalocyanine of general ruddiness blueness, painted at solvent seal China ink, solvent based coating that organic solvent content is many, comparatively high temps can be transformed into the beta-crystal of green glow blueness to coloring resin, causes tonal variation.The transformation of crystal formation does not then take place in ε-epsilon-crystal form copper phthalocyanine.Not only be suitable for printing-ink, coating and coloring plastic, and the cambial functional pigment of the electric charge that can be used for photoconductive material, be particularly useful for chromatic color filter painted in the liquid-crystal display (LCD), has excellent resistive connection crystalline substance, deflocculate stability, high transparency, brightness and specific contrast gradient.
The used starting material of the present invention be the low halo of synthetic or monochloro for the copper phthalocyanine intermediate product, have the α-epsilon-crystal form copper phthalocyanine of solvent resistance preferably, referring to accompanying drawing-1, prevent from mediating treating processes solvent alkylbenzene, to become the beta-crystal copper phthalocyanine; And has a heat-resisting and anti-solvent-stable performance that helps improve the finished product.
Show in the inventive method that if adopt common α-epsilon-crystal form copper phthalocyanine as intermediate product, mediate processing by identical control, although can obtain target product, the ε for preparing-epsilon-crystal form copper phthalocyanine shows lower heat-resisting and anti-solvent-stable performance.
The used specific alkylbenzene of the inventive method is that solvent is that Japanese AS-P2 carries out condensation reaction, prevents to become the beta-crystal copper phthalocyanine by α-epsilon-crystal form copper phthalocyanine.
Add the ε-epsilon-crystal form copper phthalocyanine of a spot of known crystal formation in the inventive method as crystal seed, can further promote under high shear action, by the conversion of α-epsilon-crystal form copper phthalocyanine intermediate product to target product ε-epsilon-crystal form copper phthalocyanine, wherein ε-epsilon-crystal form copper phthalocyanine crystal seed can be considered as the directed agents of crystal conversion.
The inventive method provides a production-scale Technology, the product yield height, the X-ray powder diffraction curve that the ε-epsilon-crystal form copper phthalocyanine product of preparation provides is located to demonstrate consistent diffracted intensity in different diffraction angle (2 θ) with known ε-epsilon-crystal form copper phthalocyanine, sees Fig. 2 and shown in Figure 3.
Claims (6)
1. the preparation technology of a ε-epsilon-crystal form copper phthalocyanine comprises:
By Tetra hydro Phthalic anhydride, chlorophthalic acid (acid anhydride), urea, cuprous chloride, synthesis of alpha-single chloro copper phthalocyanine in the presence of catalyzer;
Prepare intermediate product α-epsilon-crystal form copper phthalocyanine with vitriolization;
The kneading that utilizes kneader to carry out crystal conversion is handled;
Acid is boiled, soda boiling is handled, and filters washing, drying; Isolate pure ε-epsilon-crystal form copper phthalocyanine (C.I. pigment Blue 15: 6) product.
2. according to the preparation technology of the described a kind of ε-epsilon-crystal form copper phthalocyanine of claim 1, it is characterized in that describedly prepare the intermediate product monochloro in the copper phthalocyanine intermediate product operation with vitriolization, vitriolic concentration is 50-98%.
3. according to the preparation technology of the described a kind of ε-epsilon-crystal form copper phthalocyanine of claim 1, it is characterized in that, in the kneading treatment process of described crystal conversion, in the DEG solvent, add sodium-chlor, adopt 4000 liter kneaders of high shear force, mediated 5-10 hour.
4. according to the preparation technology of claim 1 or 3 described a kind of ε-epsilon-crystal form copper phthalocyanines, it is characterized in that the slit design between the ∑ of described kneader-shape mixing page sheet and the kneader wall is between the 0.1-0.3 millimeter.
5. according to the preparation technology of the described a kind of ε-epsilon-crystal form copper phthalocyanine of claim 1, it is characterized in that, the described utilization in the kneading treatment process that kneader carries out crystal conversion, adopting the consumption of pigment dyestuff derivative is the 5-30% of parent pigment.
6. according to the preparation technology of the described a kind of ε-epsilon-crystal form copper phthalocyanine of claim 1, it is characterized in that, the described utilization in the kneading treatment process that kneader carries out crystal conversion, the ε-epsilon-crystal form copper phthalocyanine that adds known crystal formation is as crystal seed, and amount of seed is the 5-15% of parent pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010148776A CN101817992A (en) | 2009-10-28 | 2010-03-10 | Preparation process of epsilon-crystal form copper phthalocyanine |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910075856.4 | 2009-10-28 | ||
| CN201010148776A CN101817992A (en) | 2009-10-28 | 2010-03-10 | Preparation process of epsilon-crystal form copper phthalocyanine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101817992A true CN101817992A (en) | 2010-09-01 |
Family
ID=42653275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010148776A Pending CN101817992A (en) | 2009-10-28 | 2010-03-10 | Preparation process of epsilon-crystal form copper phthalocyanine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101817992A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618065A (en) * | 2012-03-05 | 2012-08-01 | 丽王化工(南通)有限公司 | Method for manufacturing phthalocyanine blue pigment with high temperature resistance |
| CN103540164A (en) * | 2013-10-23 | 2014-01-29 | 上海捷虹颜料化工集团股份有限公司 | Blue organic pigment composition used for organic solvent system as well as preparation method thereof |
| CN103665921A (en) * | 2013-11-22 | 2014-03-26 | 宣城亚邦化工有限公司 | Method for synthetizing phthalocyanine blue BS |
| TWI460260B (en) * | 2013-02-20 | 2014-11-11 | Dainippon Ink & Chemicals | Liquid crystal display device |
| US9410084B2 (en) | 2013-06-18 | 2016-08-09 | Dic Corporation | Liquid crystal display device |
| US9442321B2 (en) | 2012-12-04 | 2016-09-13 | Dic Corporation | Liquid crystal display device |
| US9459488B2 (en) | 2013-02-21 | 2016-10-04 | Dic Corporation | Liquid crystal display device |
| US9810938B2 (en) | 2013-11-29 | 2017-11-07 | Dic Corporation | Liquid crystal display device |
| CN108373601A (en) * | 2018-02-14 | 2018-08-07 | 滨海康益医药化工有限公司 | A kind of environment-friendly type phthalocyanine blue 15:0 preparation method |
| CN109504120A (en) * | 2019-01-13 | 2019-03-22 | 滨海康益医药化工有限公司 | A kind of clean method for producing of high-purity copper phthalocyanine |
| CN110643201B (en) * | 2019-10-15 | 2021-10-22 | 河北捷虹颜料化工有限公司 | Preparation method of blue organic pigment for liquid crystal color filter material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4876925A (en) * | 1972-01-19 | 1973-10-16 | ||
| CN1061609A (en) * | 1990-11-12 | 1992-06-03 | 上海染料化工十二厂 | Solvent method for production of raw copper phthalocyanine |
| JPH0876925A (en) * | 1994-09-02 | 1996-03-22 | Kokusai Electric Co Ltd | Input / output device and control method thereof |
| JP2002121420A (en) * | 2000-08-07 | 2002-04-23 | Dainippon Ink & Chem Inc | Copper phthalocyanine pigment and method for producing the same |
| CN1827703A (en) * | 2006-04-10 | 2006-09-06 | 美利达颜料工业有限公司 | Process for preparing phthalocyanine blue 15 to 6 pigment |
| CN101457029A (en) * | 2007-12-14 | 2009-06-17 | 上海捷虹颜料化工集团股份有限公司 | Phthalocyanine blue pigment for LCD and preparation method thereof |
-
2010
- 2010-03-10 CN CN201010148776A patent/CN101817992A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4876925A (en) * | 1972-01-19 | 1973-10-16 | ||
| CN1061609A (en) * | 1990-11-12 | 1992-06-03 | 上海染料化工十二厂 | Solvent method for production of raw copper phthalocyanine |
| JPH0876925A (en) * | 1994-09-02 | 1996-03-22 | Kokusai Electric Co Ltd | Input / output device and control method thereof |
| JP2002121420A (en) * | 2000-08-07 | 2002-04-23 | Dainippon Ink & Chem Inc | Copper phthalocyanine pigment and method for producing the same |
| CN1827703A (en) * | 2006-04-10 | 2006-09-06 | 美利达颜料工业有限公司 | Process for preparing phthalocyanine blue 15 to 6 pigment |
| CN101457029A (en) * | 2007-12-14 | 2009-06-17 | 上海捷虹颜料化工集团股份有限公司 | Phthalocyanine blue pigment for LCD and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周春隆: "铜酞菁的晶型特性及其转变", 《染料工业》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618065A (en) * | 2012-03-05 | 2012-08-01 | 丽王化工(南通)有限公司 | Method for manufacturing phthalocyanine blue pigment with high temperature resistance |
| US9442321B2 (en) | 2012-12-04 | 2016-09-13 | Dic Corporation | Liquid crystal display device |
| TWI460260B (en) * | 2013-02-20 | 2014-11-11 | Dainippon Ink & Chemicals | Liquid crystal display device |
| US9459488B2 (en) | 2013-02-21 | 2016-10-04 | Dic Corporation | Liquid crystal display device |
| US9410084B2 (en) | 2013-06-18 | 2016-08-09 | Dic Corporation | Liquid crystal display device |
| CN103540164A (en) * | 2013-10-23 | 2014-01-29 | 上海捷虹颜料化工集团股份有限公司 | Blue organic pigment composition used for organic solvent system as well as preparation method thereof |
| CN103540164B (en) * | 2013-10-23 | 2015-03-11 | 上海捷虹颜料化工集团股份有限公司 | Blue organic pigment composition used for organic solvent system as well as preparation method thereof |
| CN103665921A (en) * | 2013-11-22 | 2014-03-26 | 宣城亚邦化工有限公司 | Method for synthetizing phthalocyanine blue BS |
| US9810938B2 (en) | 2013-11-29 | 2017-11-07 | Dic Corporation | Liquid crystal display device |
| CN108373601A (en) * | 2018-02-14 | 2018-08-07 | 滨海康益医药化工有限公司 | A kind of environment-friendly type phthalocyanine blue 15:0 preparation method |
| CN109504120A (en) * | 2019-01-13 | 2019-03-22 | 滨海康益医药化工有限公司 | A kind of clean method for producing of high-purity copper phthalocyanine |
| CN110643201B (en) * | 2019-10-15 | 2021-10-22 | 河北捷虹颜料化工有限公司 | Preparation method of blue organic pigment for liquid crystal color filter material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817992A (en) | Preparation process of epsilon-crystal form copper phthalocyanine | |
| Christie et al. | Phthalocyanine blue pigments | |
| EP0266219B1 (en) | Process for producing copper phthalocyanine pigment | |
| US5318623A (en) | Process for producing metal phthalocyanine pigment | |
| JPWO2020012865A1 (en) | Quinophthalone compound | |
| CN107922750A (en) | chlorinated copper phthalocyanine pigment | |
| US7211664B2 (en) | Process for the production of epsilon crystal form copper phthalocyanine | |
| CN103570734B (en) | Synthesis method of cobalt phthalocyanine diamine compound | |
| JP2005272760A (en) | ε-type crystal copper phthalocyanine and process for producing the same | |
| CN103540164B (en) | Blue organic pigment composition used for organic solvent system as well as preparation method thereof | |
| CN119463524A (en) | Blue pigment composition | |
| US4171309A (en) | Process for the preparation of a solvent-stable, red-shade copper phthalocyanine pigment composition | |
| CN103160135A (en) | Strong green light yellow disazo organic pigment | |
| JP3816766B2 (en) | Coloring composition | |
| JPH0723454B2 (en) | Method for producing copper phthalocyanine | |
| CN118978814B (en) | C.I. pigment red 224 mixed crystal and prefabricated solid, preparation method and application | |
| JP2577219B2 (en) | Method for producing copper phthalocyanine pigment | |
| CN101457031A (en) | Novel yellow light green phthalocyanine pigment for LCD color filter | |
| JP2547002B2 (en) | Method for producing copper phthalocyanine pigment | |
| JPH0336065B2 (en) | ||
| JPH011766A (en) | Method for producing copper phthalocyanine pigment | |
| JP5172345B2 (en) | New azo compounds | |
| JPH06228449A (en) | Production of metal phthalocyanine pigment | |
| JP2003012958A (en) | Coloring composition, method for producing the same, and printing ink | |
| JPH01153758A (en) | Copper phthalocyanine having novel crystal type |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100901 |