CN102516814B - High-strength yellow azo mixed pigment - Google Patents
High-strength yellow azo mixed pigment Download PDFInfo
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- CN102516814B CN102516814B CN201110441879XA CN201110441879A CN102516814B CN 102516814 B CN102516814 B CN 102516814B CN 201110441879X A CN201110441879X A CN 201110441879XA CN 201110441879 A CN201110441879 A CN 201110441879A CN 102516814 B CN102516814 B CN 102516814B
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- yellow azo
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- 239000000049 pigment Substances 0.000 title claims abstract description 182
- 238000005859 coupling reaction Methods 0.000 claims abstract description 46
- 230000008878 coupling Effects 0.000 claims abstract description 40
- 238000010168 coupling process Methods 0.000 claims abstract description 40
- 150000002148 esters Chemical group 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- -1 isobutyl- Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 150000001989 diazonium salts Chemical class 0.000 claims description 11
- 238000006193 diazotization reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UZOVPUAYHXZUNY-UHFFFAOYSA-N n-(5-acetyl-2-oxobenzimidazol-4-yl)acetamide Chemical compound CC(=O)NC1=C(C(C)=O)C=CC2=NC(=O)N=C12 UZOVPUAYHXZUNY-UHFFFAOYSA-N 0.000 claims description 9
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 2
- KQNZKBRSEJLVEO-UHFFFAOYSA-N 3-oxo-n-(2-oxobenzimidazol-5-yl)butanamide Chemical compound C1=C(NC(=O)CC(=O)C)C=CC2=NC(=O)N=C21 KQNZKBRSEJLVEO-UHFFFAOYSA-N 0.000 abstract 1
- QARVVVSRDNRWTR-UHFFFAOYSA-N N-(7-methoxyquinoxalin-6-yl)-3-oxobutanamide Chemical compound C(C)(=O)CC(=O)NC1=C(C=C2N=CC=NC2=C1)OC QARVVVSRDNRWTR-UHFFFAOYSA-N 0.000 abstract 1
- DSSKDXUDARIMTR-UHFFFAOYSA-N dimethyl 2-aminobenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(N)=C1 DSSKDXUDARIMTR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 44
- 125000000217 alkyl group Chemical group 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 5
- RJBHIXKZTPLYJU-UHFFFAOYSA-N 4-O-butyl 1-O-methyl 2-aminobenzene-1,4-dicarboxylate Chemical class COC(C1=C(C=C(C=C1)C(=O)OCCCC)N)=O RJBHIXKZTPLYJU-UHFFFAOYSA-N 0.000 description 4
- XDSRVVKROGHVAT-UHFFFAOYSA-N 4-O-butyl 1-O-methyl 2-nitrobenzene-1,4-dicarboxylate Chemical class COC(C1=C(C=C(C=C1)C(=O)OCCCC)[N+](=O)[O-])=O XDSRVVKROGHVAT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 229940035422 diphenylamine Drugs 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 0 CCNCC=C(C*CC(*N)=O)*C Chemical compound CCNCC=C(C*CC(*N)=O)*C 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003252 quinoxalines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a yellow azo mixed pigment and a preparation method thereof. The yellow azo pigment with high tinting strength is obtained by the steps of: performing ester exchange on dimethyl 2-aminoterephthalate under appropriate conditions to obtain appropriate mixed ester, performing hydrogenation reduction on the mixed ester, diazotizing, and coupling the diazotized mixed ester which is subjected to with 5-acetoacetylaminobenzimidazolone or 7-acetylacetamido-6-methoxyquinoxaline which is taken as a coupling component under appropriate conditions. The pigment has high vividness, transparency, dispersity and heat resistance, and can be used for plastics, ink and coatings.
Description
Technical field
The present invention relates to dyestuff, be specifically related to yellow azo mixed pigment of high tinctorial strength, high-clarity and preparation method thereof.
Background technology
Azo pigment refers in chemical structure the pigment dyestuff that contains azo-group (N=N-).Yellow azo pigment is class cheapness and the higher pigment dyestuff of tinting strength.The light fastness that yellow azo pigment has had also is applicable in paint and printing ink.But, while using in plastics, yellow azo pigment at high temperature easy frosting causes tinting strength to descend, and resistance to migration is poor.
The diphenyl amine Yellow disazo pigment has very high tinting strength and resistance to migration and thermotolerance preferably.C.I. pigment yellow 17 is a kind of diphenyl amine pigment of green glow yellow, is often used in plastics.Its heat resisting temperature can reach 240 ℃.Due to p-diaminodiphenyl pigment, when temperature reaches more than 200 ℃, can produce objectionable impurities (for example, 3,3 '-dichlorobenzidine), human body is had to carcinogenic danger.
C.I. pigment yellow 17 5 (a kind of monoazo pigment obtained through diazotization and the coupling of 5-ethanoyl acetamino benzimidazolone by the amino dimethyl terephthalate (DMT) of 2-) is a kind of both economical kind, does not contain the forbidding arylamine, to human body without potential hazard.Have strong green glow yellow, hue angle is 97.9 degree (1/3SD), and excellent in light-resistance, have excellent weather resistance; Be mainly used in car paint and retouching paint; When coloring plastic, thermostability is high, can be used for hard PVC painted; Also can be used for high-grade seal China ink painted.
C.I. Pigment Yellow 73 213 (a kind of azo pigment obtained through diazotization and the coupling of 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-Jia oxygen based quinoxaline by the amino dimethyl terephthalate (DMT) of 2-) does not contain the forbidding arylamine, to human body without potential hazard.Because molecule contains amido, make it there is good light fastness and heat-resistant stability, its heat-resistant stability reaches 290 ℃, is mainly used in plastics and fabric printing.
But, with p-diaminodiphenyl pigment, to compare, still there are the problem of low strength in above-mentioned C.I. pigment yellow 17 5 and C.I. Pigment Yellow 73 213 these two kinds of pigment, hinder its a large amount of uses.For example, with the C.I. pigment yellow 17, compare C.I. pigment yellow 17 5 low strength 20 minutes.Improve the tinctorial strength of these two kinds of pigment, likely substitute diphenyl amine pigment.
Summary of the invention
The inventor is through research discovery with keen determination; by being carried out to transesterify under proper condition, the amino dimethyl terephthalate (DMT) of 2-obtains suitable mixed ester; then by the mixed ester hydro-reduction; after diazotization under proper condition with 5-ethanoyl acetamino benzimidazolone or the coupling of 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-first oxygen based quinoxaline as the coupling composition; obtain having the azophosphine hybrid pigment of high tinctorial strength, complete thus the present invention.
The first purpose of the present invention is to provide a kind of yellow azo mixed pigment, and following formula (2) pigment compound of its following formula by 70 % by weight-95 % by weight (1) pigment compound and 30 % by weight-5 % by weight forms,
Wherein, the weight sum of described weight ratio based on formula (1) pigment compound and formula (2) pigment compound,
R
1for methyl,
R
2be selected from alkyl.
The second purpose of the present invention is to provide the preparation method of the described yellow azo mixed pigment of above-mentioned the first purpose, and the method comprises the following steps:
(1) under the acidic catalyst condition, 2-nitro dimethyl terephthalate (DMT) is carried out transesterify in alcohol, obtains the 2-nitro terephthalic acid mixed ester of following formula (3) and (4)
(2), by above-mentioned 2-nitro terephthalic acid mixed ester hydro-reduction, obtain the amino terephthalic acid mixed ester of 2-of corresponding following formula (5) and (6)
(3) by the amino terephthalic acid mixed ester of above-mentioned 2-diazotization at the temperature of 0-10 ℃;
(4) will be dissolved in as the 5-ethanoyl acetamino benzimidazolone of coupling composition the aqueous solution of sodium hydroxide, add emulsifying agent, obtain coupling solution, add sodium bicarbonate again in water at the bottom of coupling, at the temperature of 0-30 ℃, gained diazonium compound in step (3) and coupling solution drip are added at the bottom of coupling in water, after reaction finishes, be warming up at the temperature of 85-95 ℃ and be incubated, obtain yellow azo mixed pigment after filtration washing;
Wherein, R
1for methyl,
R
2be selected from alkyl.
The 3rd purpose of the present invention is to provide a kind of yellow azo mixed pigment, and following formula (12) pigment compound of its following formula by 70 % by weight-95 % by weight (11) pigment compound and 30 % by weight-5 % by weight forms,
Wherein, the weight sum of described weight ratio based on formula (11) pigment compound and formula (12) pigment compound,
R
1for methyl,
R
2be selected from alkyl.
The 4th purpose of the present invention is to provide the preparation method of the described yellow azo mixed pigment of above-mentioned the 3rd purpose, and the method comprises the following steps:
(1) under the acidic catalyst condition, 2-nitro dimethyl terephthalate (DMT) is carried out transesterify in alcohol, obtains the 2-nitro terephthalic acid mixed ester of following formula (3) and (4)
(2), by above-mentioned 2-nitro terephthalic acid mixed ester hydro-reduction, obtain the amino terephthalic acid mixed ester of 2-of corresponding following formula (5) and (6)
(3) by the amino terephthalic acid mixed ester of above-mentioned 2-diazotization at the temperature of 0-10 ℃;
(4) will be dissolved in as the 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-first oxygen base quinoline Evil of coupling composition the aqueous solution of sodium hydroxide, add emulsifying agent, obtain coupling solution, add sodium bicarbonate again in water at the bottom of coupling, at the temperature of 0-30 ℃, gained diazonium compound in step (3) and coupling solution drip are added at the bottom of coupling in water, after reaction finishes, be warming up at the temperature of 85-95 ℃ and be incubated, obtain yellow azo mixed pigment after filtration washing;
Wherein, R
1for methyl,
R
2be selected from alkyl.
According to yellow azo mixed pigment provided by the invention, vividness is good, and tinctorial strength is high, and transparency is high, and dispersed high, thermotolerance is good, can be for plastics, printing ink and coating.
Embodiment
Below by drawings and Examples, invention is carried out.The features and advantages of the invention will become more clear, clear and definite along with these descriptions.
first aspect
According to a first aspect of the invention, provide a kind of yellow azo mixed pigment, following formula (2) pigment compound of its following formula by 70 % by weight-95 % by weight (1) pigment compound and 30 % by weight-5 % by weight forms,
Wherein, the weight sum of described weight ratio based on formula (1) pigment compound and formula (2) pigment compound,
R
1for methyl,
R
2be selected from alkyl, preferably there is the alkyl of 1-10 carbon atom, more preferably there is the alkyl of 1-6 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl etc., most preferably normal-butyl.
In the preferred embodiment of the yellow azo mixed pigment according to first aspect present invention, described yellow azo mixed pigment is comprised of formula (1) pigment compound of 85 % by weight-95 % by weight and formula (2) pigment compound of 15 % by weight-5 % by weight, more preferably by formula (1) pigment compound of 85 % by weight or 95 % by weight and formula (2) pigment compound of 15 % by weight or 5 % by weight, formed, the weight sum of described weight ratio based on formula (1) pigment compound and formula (2) pigment compound, its Chinese style (1) and (2) described as defined above.
In the further preferred embodiment of the yellow azo mixed pigment according to first aspect present invention, described yellow azo mixed pigment is comprised of formula (1) pigment compound of 85 % by weight-95 % by weight and formula (2) pigment compound of 15 % by weight-5 % by weight, more preferably formula (1) pigment compound of 85 % by weight or 95 % by weight and formula (2) pigment compound of 15 % by weight or 5 % by weight, consists of
Wherein, R
1for methyl,
R
2for normal-butyl.
second aspect
According to a second aspect of the invention, provide the preparation method of the mixed pigment of the described yellow azo of above-mentioned first aspect, the method comprises the following steps:
(1) under the acidic catalyst condition, 2-nitro dimethyl terephthalate (DMT) is carried out transesterify in alcohol, obtains the 2-nitro terephthalic acid mixed ester of following formula (3) and (4)
(2), by above-mentioned 2-nitro terephthalic acid mixed ester hydro-reduction, obtain the amino terephthalic acid mixed ester of 2-of corresponding following formula (5) and (6)
(3) by the amino terephthalic acid mixed ester of above-mentioned 2-diazotization at the temperature of 0-10 ℃;
(4) will be dissolved in as the 5-ethanoyl acetamino benzimidazolone of coupling composition the aqueous solution of sodium hydroxide, add emulsifying agent, obtain coupling solution, add sodium bicarbonate again in water at the bottom of coupling, at the temperature of 0-30 ℃, gained diazonium compound in step (3) and coupling solution drip are added at the bottom of coupling in water, after reaction finishes, be warming up at the temperature of 85-95 ℃ and be incubated, obtain yellow azo mixed pigment after filtration washing;
Wherein, R
1for methyl,
R
2be selected from alkyl, preferably there is the alkyl of 1-10 carbon atom, more preferably there is the alkyl of 1-6 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl etc., most preferably normal-butyl.
In the embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, in step (1), alcohol used is R
2with the alcohol that hydroxyl forms, preferably there is the alcohol of 1-10 carbon atom, more preferably there is the alcohol of 1-6 carbon atom, such as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol and hexanol etc., most preferably propyl carbinol.
In the preferred embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, in step (1), described acidic conditions is the mineral acid condition, under the condition existed at sulfuric acid, phosphoric acid or boric acid etc.Experiment shows, under affiliated acidic conditions, due to the suction of nitro, electrically on the impact of ortho position ester group, alcoholysis can occur, and in corresponding solvent system, transesterify occurs; And nitro between the impact of position ester group less, therefore under described condition, alcoholysis does not occur in a position ester group substantially, and transesterification reaction does not occur.
In the preferred embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, in step (1), while carrying out transesterification reaction, need control the reaction times and/or monitored by liquid chromatography, with the degree of guaranteeing that transesterification reaction is carried out, make the 2-nitro dimethyl terephthalate (DMT) of 5-30 % by weight carry out transesterify.
In the embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, in step (2), the hydro-reduction of 2-nitro terephthalic acid mixed ester can be undertaken by catalysis, for example on the Pt/C catalyzer, carries out.
In the embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, in step (3), the diazotization of the amino terephthalic acid mixed ester of 2-can be undertaken by ordinary method, for example, under hydrochloric acid exists, carry out diazotization by dripping sodium nitrite solution, the diazotization temperature is 0-10 ℃, preferably 0-5 ℃.
In the embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, in step (4), to be dissolved in as the 5-ethanoyl acetamino benzimidazolone of coupling composition the aqueous solution of sodium hydroxide, add emulsifying agent as fatty alcohol-polyoxyethylene ether, obtain coupling solution, add sodium bicarbonate in water at the bottom of coupling, at 0-30 ℃, preferably at the temperature of 15-25 ℃, gained diazonium compound in step (3) and coupling solution drip are added at the bottom of coupling in water, after reaction finishes, be warming up at the temperature of 85-95 ℃ and be incubated, obtain yellow azo mixed pigment after filtration washing.
In order to promote coupled reaction fully to carry out, can use micro-excessive coupling solution.
Whether react completely in order to monitor diazonium salt, can detect with H acid (1-amino-8-naphthol-3,6-disulfonic acid).
In the preferred embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, after coupled reaction finishes, preferably heat-treat, so that the gained hybrid pigment has good vividness, high tinctorial strength and dispersiveness.3-5 hour is for example carried out in described thermal treatment under reflux temperature, or carries out several minutes-a few hours under High Temperature High Pressure, can when thermal treatment, add the rosin soap lye.
In the preferred embodiment of the yellow azo mixed pigment preparation method according to second aspect present invention, after reaction and thermal treatment, the suspension liquid of gained yellow ultramarine is filtered, washing, dry, and pulverizes, obtain yellow hybrid pigment fine powder, it is easy to be scattered among applicating medium.
the third aspect
According to the 3rd invention of the present invention, a kind of yellow azo mixed pigment is provided, following formula (12) pigment compound of its following formula by 70 % by weight-95 % by weight (11) pigment compound and 30 % by weight-5 % by weight forms,
Wherein, the weight sum of described weight ratio based on formula (11) pigment compound and formula (12) pigment compound,
R
1for methyl,
R
2be selected from alkyl, preferably there is the alkyl of 1-10 carbon atom, more preferably there is the alkyl of 1-6 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl etc., most preferably normal-butyl.
In the preferred embodiment of the yellow azo mixed pigment according to third aspect present invention, described yellow azo mixed pigment is comprised of formula (11) pigment compound of 85 % by weight-95 % by weight and formula (12) pigment compound of 15 % by weight-5 % by weight, more preferably by formula (11) pigment compound of 85 % by weight or 95 % by weight and formula (22) pigment compound of 15 % by weight or 5 % by weight, formed, the weight sum of described weight ratio based on formula (11) pigment compound and formula (12) pigment compound, formula (11) and (12) described as defined above.
In the further preferred embodiment of the yellow azo mixed pigment according to first aspect present invention, described yellow azo mixed pigment is comprised of formula (11) pigment compound of 85 % by weight-95 % by weight and formula (12) pigment compound of 15 % by weight-5 % by weight, more preferably formula (11) pigment compound of 85 % by weight or 95 % by weight and formula (12) pigment compound of 15 % by weight or 5 % by weight, consists of
Wherein, R
1for methyl,
R
2for normal-butyl.
fourth aspect
The preparation method of the described yellow azo mixed pigment of the above-mentioned third aspect is provided according to a forth aspect of the invention.
Described preparation and concrete, preferred embodiment thereof be with identical in above-mentioned " second aspect ", and difference only is, in this " fourth aspect " as coupling composition use 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-first oxygen based quinoxaline.
embodiment
Below by specific embodiment, the present invention is described further, but these embodiment are only exemplary, should not understand limitation of the present invention.
the preparation of the amino terephthalic acid mixed ester of embodiment 1 2-
30 gram 2-nitro dimethyl terephthalate (DMT) are joined in 300 milliliters of butanols, then add the 0.1 gram vitriol oil, reflux and keep 5 hours, detecting the gained material through high performance liquid chromatography is the mixed ester that contains 2-nitro dimethyl terephthalate (DMT) and 2-nitro-4-n-butoxy carbonyl benzoic acid methyl esters, the content of mixed ester is 99.3%, and wherein the part by weight of 2-nitro dimethyl terephthalate (DMT) and 2-nitro-4-n-butoxy carbonyl benzoic acid methyl esters is 95: 5.
Be cooled to normal temperature, above-mentioned reactant is dosed to autoclave, add 3% palladium-carbon catalyst of 0.1 gram, under 110 ℃, pass into hydrogen, under 0.2mpa, reaction is 10 hours.Be cooled to 90 ℃, heat filtering, reclaim palladium-carbon catalyst.Collect mother liquor, be cooled to normal temperature, standing 5 hours, filter, washing, dry, and obtains the mixed ester 25.16g of the amino dimethyl terephthalate (DMT) of 2-and 2-amino-4-n-butoxy carbonyl benzoic acid methyl esters, the content that high performance liquid chromatography detects mixed ester is 99.7%, and wherein the part by weight of the amino dimethyl terephthalate (DMT) of 2-and 2-amino-4-n-butoxy carbonyl benzoic acid methyl esters is 95: 5.
the preparation of the amino terephthalic acid mixed ester of embodiment 2 2-
30 gram 2-nitro dimethyl terephthalate (DMT) are joined in 300 milliliters of butanols, then add the 0.15 gram vitriol oil, reflux and keep 11 hours, high performance liquid chromatography detects the mixed ester that contains 2-nitro dimethyl terephthalate (DMT) and 2-nitro-4-n-butoxy carbonyl benzoic acid methyl esters, the content of mixed ester is 99.8%, and wherein the part by weight of 2-nitro dimethyl terephthalate (DMT) and 2-nitro-4-n-butoxy carbonyl benzoic acid methyl esters is 85: 15.
Be cooled to normal temperature, reactant is dosed to autoclave, add 3% palladium-carbon catalyst of 0.1 gram, under 110 ℃, pass into hydrogen, under 0.2mpa, reaction is 10 hours.Be cooled to 90 ℃, heat filtering, reclaim palladium-carbon catalyst.Collect mother liquor, be cooled to normal temperature, standing 5 hours, filter, washing, dry, and obtains the mixed ester 25.19g of the amino dimethyl terephthalate (DMT) of 2-and 2-amino-4-n-butoxy carbonyl benzoic acid methyl esters, the content that high performance liquid chromatography detects mixed ester is 99%, and wherein the part by weight of the amino dimethyl terephthalate (DMT) of 2-and 2-amino-4-n-butoxy carbonyl benzoic acid methyl esters is 85: 15.
the preparation of embodiment 3 yellow azo mixed pigments
Gained mixed ester in 10 gram embodiment 1 is joined in 340 ml waters, then add 16 gram 35% hydrochloric acid, keep 8 hours.The 0-5 ℃ that is cooled on the rocks, add 20% sodium nitrite solution 17.2 grams fast, keeps 1 hour.By solution filter, collect mother liquor, obtain diazonium salt solution.
11.05 gram 5-ethanoyl acetamino benzimidazolones and 3.8 gram sodium hydroxide are joined to 73 ml waters, be stirred to whole dissolvings.Add 0.3 gram ethoxylated dodecyl alcohol, stir 10 minutes, and temperature is remained on to 15-20 ℃, obtain coupling solution.Adjust diazonium salt identical with the coupling solution volume.
Adding 4.2 gram sodium bicarbonates in 250mL water, after stirring and dissolving, is under 15-25 ℃ and drip adds diazonium salt solution and coupling solution carries out coupling in temperature, within about 30 minutes, adds.Extract reaction solution 1, drip on filter paper, ooze circle one side at it and drip the H acid solution, it is excessive if do not developed the color, to show without diazonium salt, and reaction finishes; If aobvious red, must add coupling solution.Obtain yellow slurry.
Be warming up to 90 ℃, keep 4 hours, filtered while hot, be washed to neutrality, after filter cake drying, pulverizing, obtains yellow hybrid pigment 20.7 grams, yield 96.8%.
The results of elemental analyses of hybrid pigment:
C:55.86%, H:4.31%, O:24.39%, N:15.43%, the hybrid pigment molecular ratio is C: H: O: N=21.11: 19.42: 6.92: 5, meet the hybrid pigment that two kinds of pigment weight ratios are 95: 5 and form.From product yield, the coupled catalytic conversion rate reaches 96.8%, and intermediate two component ratios are very definite, and that coupled reaction obtains pigment structure is very definite, can assert in the intermediate ratio and form hybrid pigment.
the preparation of embodiment 4 yellow azo mixed pigments
In using 10.2 gram embodiment 2, the gained mixed ester replaces in 10 gram embodiment 1, the gained mixed ester, with method in the same manner as in Example 3, preparing yellow azo mixed pigment.Obtain yellow hybrid pigment 20.7 grams, yield 96.5%.
The results of elemental analyses of hybrid pigment:
C:56.27%, H:4.36%, O:24.11%, N:15.25%, the hybrid pigment molecular ratio is C: H: O: N=21.51: 19.87: 6.92: 5, meet two kinds of pigment and take the hybrid pigment that weight ratio is 85: 15 and form.From product yield, the coupled catalytic conversion rate reaches 96.5%, and intermediate two component ratios are very definite, and that coupled reaction obtains pigment structure is very definite, can assert in the intermediate ratio and form hybrid pigment.
the preparation of embodiment 5 yellow azo mixed pigments
Except using the alternative 11.05 gram 5-ethanoyl acetamino benzimidazolones of 13.8 gram 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-Jia oxygen based quinoxalines, with method in the same manner as in Example 3, prepare yellow azo mixed pigment.Obtain yellow hybrid pigment 23.8 grams, yield 97.0%.
The results of elemental analyses of hybrid pigment:
C:54.38%, H:4.15%, O:27.78%, N:13.68%, the hybrid pigment molecular ratio is C: H: O: N=23.18: 21.09: 8.89: 5, meet two kinds of pigment and form with the weight ratio hybrid pigment of 95: 5.From product yield, the coupled catalytic conversion rate reaches 97.0%, and intermediate two component ratios are very definite, and that coupled reaction obtains pigment structure is very definite, can assert in the intermediate ratio and form hybrid pigment.
the preparation of embodiment 6 yellow azo mixed pigments
Except using 13.8 gram 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-Jia oxygen based quinoxalines to substitute 11.05 gram 5-ethanoyl acetamino benzimidazolones; with use in 10.2 gram embodiment 2 the gained mixed ester to replace in 10 gram embodiment 1, beyond the gained mixed ester, with method in the same manner as in Example 3, preparing yellow azo mixed pigment.Obtain yellow hybrid pigment 23.9 grams, yield 96.8%.
The results of elemental analyses of hybrid pigment:
C:54.56%, H:4.25%, O:27.68%, N:13.51%, the hybrid pigment molecular ratio is C: H: O: N=23.55: 21.85: 8.97: 5, meet two kinds of pigment and form with the weight ratio hybrid pigment of 85: 15.From product yield, the coupled catalytic conversion rate reaches 96.8%, and intermediate two component ratios are very definite, and that coupled reaction obtains pigment structure is very definite, can assert in the intermediate ratio and form hybrid pigment.
test example
compare coloured light, intensity and thermotolerance in polyethylene
With p-diaminodiphenyl pigment 1124 permanent fixed yellow GGs (C.I. pigment yellow 17), Hostaperm Yellow H6G (C.I. pigment yellow 17 5) and Hostaperm Yellow H56 (C.I. Pigment Yellow 73 213), compare, the pigment that testing standard selects Hostaperm Yellow H6G (C.I. pigment yellow 17 5) and Hostaperm Yellow H56 (C.I. Pigment Yellow 73 213) to produce for Clariant company.
Coloured light comparative approach: get 0.2 gram pigment sample, evenly spread in 200 gram HDPE (2911 type) resin, in 200-220 ℃ of moulding on injection moulding machine, then use under D65/10 ° of color measurement instrument (thinking scholar) the relatively color distortion of each pigment.The results are shown in following table 1.
Intensity comparative approach: get 0.2 gram pigment sample, add 1.0 gram TiO
2(E.I.Du Pont Company, R-902), evenly spread in 200 gram HDPE resins, in 200-220 ℃ of moulding on injection moulding machine, then with the color measurement instrument strength difference of each pigment relatively.The results are shown in following table 1.
Method for Measuring Heat-resistibility: get 0.2 gram pigment sample, add 1.0 gram TiO
2(E.I.Du Pont Company, R-902), evenly spread in 200 gram HDPE resins, keeps 5min under 260 ℃, moulding on injection moulding machine.Detect heating front and back chromatic aberration with color measurement instrument.Thermally-stabilised data are Δ E changing value.The results are shown in following table 1.
Table 1 coloured light, intensity and thermotolerance detected result
As shown in Table 1, in example 3,4, the tinctorial strength of the yellow hybrid pigment of gained improves approximately more than 10% than pigment yellow 17 5, and coloured light approaches pigment yellow 17 5.From heat-resisting stable data, its thermotolerance is suitable with pigment yellow 17 5, and heat resisting temperature can reach 260 ℃.
In example 5,6, the tinctorial strength of the yellow hybrid pigment of gained improves approximately more than 10% than Pigment Yellow 73 213, and coloured light approaches Pigment Yellow 73 213.From heat-resisting stable data, its thermotolerance is suitable with Pigment Yellow 73 213, and heat resisting temperature can reach 260 ℃.In polyethylene, use, the pigment that the present invention obtains has high tinctorial strength and green glow yellow, and thermotolerance is better, meets the painted requirement of plastic cement.
Claims (11)
1. a yellow azo mixed pigment, following formula (2) pigment compound of its following formula by 70 % by weight-95 % by weight (1) pigment compound and 30 % by weight-5 % by weight forms,
Wherein, the weight sum of described weight ratio based on formula (1) pigment compound and formula (2) pigment compound,
R
1for methyl,
R
2be selected from propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl.
2. yellow azo mixed pigment according to claim 1, wherein R
2for normal-butyl.
3. yellow azo mixed pigment according to claim 1, described yellow azo mixed pigment is comprised of formula (1) pigment compound of 85 % by weight-95 % by weight and formula (2) pigment compound of 15 % by weight-5 % by weight.
4. yellow azo mixed pigment according to claim 1, described yellow azo mixed pigment is comprised of formula (1) pigment compound of 85 % by weight or 95 % by weight and formula (2) pigment compound of 15 % by weight or 5 % by weight
Wherein, R
1for methyl,
R
2for normal-butyl.
5. a yellow azo mixed pigment, following formula (12) pigment compound of its following formula by 70 % by weight-95 % by weight (11) pigment compound and 30 % by weight-5 % by weight forms,
Wherein, the weight sum of described weight ratio based on formula (11) pigment compound and formula (12) pigment compound,
R
1for methyl,
R
2be selected from propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl.
6. yellow azo mixed pigment according to claim 5, wherein R
2for normal-butyl.
7. according to yellow azo mixed pigment claimed in claim 5, described yellow azo mixed pigment is comprised of formula (11) pigment compound of 85 % by weight-95 % by weight and formula (12) pigment compound of 15 % by weight-5 % by weight.
8. yellow azo mixed pigment according to claim 5, described yellow azo mixed pigment is comprised of formula (11) pigment compound of 85 % by weight or 95 % by weight and formula (12) pigment compound of 15 % by weight or 5 % by weight
Wherein, R
1for methyl,
R
2for normal-butyl.
9. according to the preparation method of claim 1 or 5 described yellow azo mixed pigment, the method comprises the following steps:
(1) under the acidic catalyst condition, 2-nitro dimethyl terephthalate (DMT) is carried out transesterify in alcohol, obtains the 2-nitro terephthalic acid mixed ester of following formula (3) and (4), and alcohol used is R
2propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol or hexanol with hydroxyl formation
(2), by above-mentioned 2-nitro terephthalic acid mixed ester hydro-reduction, obtain the amino terephthalic acid mixed ester of 2-of corresponding following formula (5) and (6)
(3) by the amino terephthalic acid mixed ester of above-mentioned 2-diazotization at the temperature of 0-10 ℃;
(4) aqueous solution that will be dissolved in sodium hydroxide as 5-ethanoyl acetamino benzimidazolone or the 7-ethanoyl acetylaminohydroxyphenylarsonic acid 6-first oxygen based quinoxaline of coupling composition, add emulsifying agent, obtain coupling solution, add sodium hydrogen carbonate solution again in coupling solution, at the temperature of 0-30 ℃, gained diazonium compound in step (3) and coupling solution drip are added at the bottom of coupling in water, after reaction finishes, be warming up at the temperature of 85-95 ℃ and be incubated, obtain yellow azo mixed pigment after filtration washing;
Wherein, R
1for methyl,
R
2be selected from propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl.
10. method according to claim 9,
In step (3), carry out diazotization at the temperature of 0-5 ℃; And/or
In step (4), at the temperature of 15-25 ℃, gained diazonium compound in step (3) and coupling solution drip are added at the bottom of coupling in water;
In step (4) afterwards, heat-treat; And/or
Add the rosin soap lye when heat-treating.
11. method according to claim 10, in step (1), alcohol used is propyl carbinol.
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