CN1064384C - 鲜明的铜酞菁颜料的制造方法 - Google Patents
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- 239000000049 pigment Substances 0.000 title claims abstract description 24
- 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 22
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920006391 phthalonitrile polymer Polymers 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkyl xylene Chemical compound 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 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
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- YFRGOBSBDSYRNN-UHFFFAOYSA-N 1-butyl-2,3-dimethylbenzene Chemical group CCCCC1=CC=CC(C)=C1C YFRGOBSBDSYRNN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 230000006209 tert-butylation Effects 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- VAUOSVQRIKZEJF-UHFFFAOYSA-N 1-butan-2-yl-2,3-dimethylbenzene Chemical compound CCC(C)C1=CC=CC(C)=C1C VAUOSVQRIKZEJF-UHFFFAOYSA-N 0.000 description 2
- GKGTVJOYFGUPSA-UHFFFAOYSA-N 2,4-dimethylpentan-3-ylbenzene Chemical compound CC(C)C(C(C)C)C1=CC=CC=C1 GKGTVJOYFGUPSA-UHFFFAOYSA-N 0.000 description 2
- ZRJNQRHSLVSHNI-UHFFFAOYSA-N 2-butyl-1,4-dimethylbenzene Chemical group CCCCC1=CC(C)=CC=C1C ZRJNQRHSLVSHNI-UHFFFAOYSA-N 0.000 description 2
- ZRSAYHZFGWKIFQ-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonitrile Chemical compound N#CC1=CC=CC(C=2C=CC=CC=2)=C1C#N ZRSAYHZFGWKIFQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- STQPCKPKAIRSEL-UHFFFAOYSA-N 2-cyanobenzamide Chemical compound NC(=O)C1=CC=CC=C1C#N STQPCKPKAIRSEL-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229940055858 aluminum chloride anhydrous Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229950008475 oxophenarsine Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G08—SIGNALLING
- G08G—TRAFFIC CONTROL SYSTEMS
- G08G1/00—Traffic control systems for road vehicles
- G08G1/01—Detecting movement of traffic to be counted or controlled
- G08G1/0104—Measuring and analyzing of parameters relative to traffic conditions
- G08G1/0108—Measuring and analyzing of parameters relative to traffic conditions based on the source of data
- G08G1/012—Measuring and analyzing of parameters relative to traffic conditions based on the source of data from other sources than vehicle or roadside beacons, e.g. mobile networks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
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- G06Q50/40—Business processes related to the transportation industry
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- G—PHYSICS
- G08—SIGNALLING
- G08G—TRAFFIC CONTROL SYSTEMS
- G08G1/00—Traffic control systems for road vehicles
- G08G1/01—Detecting movement of traffic to be counted or controlled
- G08G1/0104—Measuring and analyzing of parameters relative to traffic conditions
- G08G1/0137—Measuring and analyzing of parameters relative to traffic conditions for specific applications
- G08G1/0141—Measuring and analyzing of parameters relative to traffic conditions for specific applications for traffic information dissemination
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Abstract
本发明提供了一种铜酞菁颜料的制造方法及铜酞菁颜料制造用反应溶剂,在反应中不必设定加压条件,且颜料的收率高,制得的颜料的色调鲜明,适于工业上的大量生产。该铜酞菁颜料的制造方法的特征在于,在将苯二酸或其衍生物与尿素及含铜物质,或酞腈或其衍生物与含铜物质在反应溶剂中进行加热反应制造铜酞菁颜料的方法中,使用以下式(1)
表示的带有支链型C4侧链的烷基二甲苯成分作为该反应溶剂。
Description
本发明涉及具有鲜明色调的在工业上非常重要的铜酞菁颜料的制造方法。
铜酞菁颜料因其色调优美、粘着力强、耐气候性、耐热性、耐溶剂性、耐化学性等优良,因此在色素材料工业领域广泛使用,被大量制造。
虽然已经提出了多种作为有用颜料的铜酞菁颜料的合成方法,但工业制造方法中目前多采用以下方法:(1)将苯二酸、苯二酸酐或酞酰亚胺等与尿素及铜或铜盐在对反应呈惰性的溶剂中进行反应的苯二酸溶剂法及(2)将酞腈与铜或铜盐在对反应呈惰性的溶剂中进行反应的腈溶剂法。此外,还有(3)邻氰基苯酰胺与铜或铜盐的反应,(4)无金属酞菁与铜盐的反应等。
作为这些反应的溶剂,先前使用的有氯苯类(如美国专利第4140695号)等,但因为是卤化溶剂,所以从臭味方面考虑有保护作业环境的必要性,进而进行了各种改善。作为其中的改善之一是提出了不使用含卤素反应溶剂,如在特开昭49-63735号公报中记载的以二异丙基甲苯或二异丙基甲苯作为主成分的混合溶剂及在特开昭49-116121号公报中记载的以在常压下具有160-250℃温度范围沸点的聚烷基苯中的在苯核上带有由含有至少1个异丙基的2个以上的低级烷基构成的取代基的聚烷基苯作为溶剂的方法等。
在铜酞菁颜料的制造中,要能够确保在颜料制造时的充分的反应温度及必须有对于苯二酸酐及酞菁等颜料合成原料或中间体具有充分的溶解性的溶剂,且在反应结束时必须能够使制得的颜料与使用的溶剂顺利分离。
在工业上,作为该分离工序将反应溶剂蒸发分离是按一般方法进行的。为使该蒸发分离容易且经济地进行,要求制造颜料用的反应溶剂的沸点范围不宜过宽及沸点不宜过高。
但在先前提出的上述方法中,因为溶剂的沸点低,为提高溶解性及确保反应温度,在颜料的制造时不得不设定加压条件,相反在沸点过高的情况下,在回收溶剂时必须要有必要以上的加热及减压条件。
此外,制得的颜料的收率及该颜料的鲜明度等也未必能够满足要求。
本发明的目的在于,提供铜酞菁颜料制造用反应溶剂及铜酞菁颜料的制造方法,可解决现有技术中存在的技术问题,没有必要在反应时设定加压条件,且颜料的收率高,另外制得的颜料的色调鲜明,适合工业上的大量生产。
本发明人等对颜料制造中适用的反应溶剂进行了研究,结果发现了具有较先前的溶剂更优良的性状的溶剂,完成了本发明。
本发明的铜酞菁颜料制造方法的特征在于,在将苯二酸酐或其衍生物与尿素及含有铜的物质、或酞菁或其衍生物与含有铜的物质在溶剂中进行加热反应以制造铜酞菁颜料的方法中,使用以式(1)表示的带有支链型C4侧链的烷基二甲苯成分作为该溶剂。
以下详细说明本发明。
本发明的铜酞菁颜料的制造,是通过向反应中供给苯二酸酐或其衍生物进行反应。苯二酸酐衍生物例如有邻苯二酸二酰胺、酞氨基酸、酞酰亚胺及苯二酸酐或具有衍生物的在苯核上被氯、溴等卤素原子取代的卤素核取代物或被甲基、乙基等烷基取代的烷基核取代物等。即,苯二酸酐、苯二酸酐衍生物或酞腈及其衍生物等,具有对应于所得到的希望类型的铜酞菁颜料的取代基。
作为尿素类可以使用尿素,也可以使用缩二脲、缩三脲等尿素衍生物。此外,作为含铜物质例如有铜或氯化铜、硫酸铜、醋酸铜等铜盐。
另外,也可以使用酞腈及苯基酞腈等及其衍生物,使与含铜物质反应。作为含铜物质与上述相同,例如有铜或氯化铜、硫酸铜、醋酸铜等铜盐。
不是在任何情况下都必须使用催化剂,但根据需要可以适当使用氧化钼、钼酸铵、羰基合钼等钼化合物、氧化砷等化合物或硼酸等。
上述原料的使用比例为,相对于苯二酸或其衍生物,铜或铜盐等含铜物质为10-30摩尔%、尿素类为50-500摩尔%、本发明的溶剂为1-10重量倍左右、根据需要添加的催化剂为0.1重量倍左右。相对于酞腈或苯基酞腈等的衍生物,铜或铜盐等含有铜的物质为10-30摩尔%、本发明的溶剂为1-10重量倍左右、根据需要添加的催化剂为0.1重量倍左右。
在本发明中,使用以上述式(1)表示的叔丁基二甲苯作为反应溶剂。带有具有该特定构造的支链型C4侧链的烷基二甲苯类,例如有将邻、间、对型二甲苯分别进行叔丁基化衍生得到的叔丁基邻二甲苯、叔丁基间二甲苯、叔丁基对二甲苯等。其中,从简便且价廉地可以得到化合物方面考虑,优选叔丁基邻二甲苯。
上述的叔丁基二甲苯的制造方法无特别限定,可以使用通过公知的任意方法制得的产物。也可以使用例如在氯化铝、氟化硼等酸催化剂存在下,由异丁烯将邻、间、对二甲苯或这些的混合物叔丁基化的方法制得的物质。
本发明中,上述叔丁基二甲苯可以单独或适当混合使用。即,在上述反应溶剂中投入苯二酸酐或其衍生物、尿素及含铜物质,或酞腈或其衍生物与含铜物质,进行加热反应。含有反应溶剂的各反应原料的投入顺序等无特别限制。通常以同时向反应系统内供给为好。
另外,根据需要也可与其他的公知的溶剂混合,对于其他溶剂无特别限制,但优选与本发明的溶剂的沸点相近的溶剂。
如果使用本发明的带有具有特定构造的支链型C4侧链的烷基二甲苯类,则没有必要为确保铜酞菁颜料制造时的反应温度而将装置特别加压,也没有必要在装置上设置特别的附带设备。另外,因为没有必要在高温加压下处理大量的可燃性物质,所以容易确保安全性。这在装置运转时提高安全性方面以及在实用上是非常有益的。
另外,本发明的带有具有特定构造的支链型C4侧链的烷基二甲苯类,与其他的具有骨架构造的溶剂相比,相对于加入原料而得到的颜料的收率提高,优选作为实用溶剂。提高收率的原因不明,但可认为是由于相对于苯环的取代烷基数较多及由于分支度高而对原料及中间体的溶解性高,促进了颜料的生成反应。
在进行本发明的制造方法时,将原料、反应溶剂及根据需要使用的催化剂加入至高压釜等耐压容器内,在搅拌下进行加热搅拌。
对反应温度无特别限定,例如为130-300℃,优选从150-300℃左右的范围适当选择。如果使用本发明的溶剂,则反应压力不必特别加压,可在本来的压力下使反应进行。当然也可以通过导入惰性气体等适当加压,其压力无特别限定,例如可从30kg/cm2以下的压力适当选择。
反应时间也无特别限定,但通常在30-200分钟的范围内结束。
反应结束后,利用常法,进行中和、水洗等,可以得到作为目的产物的铜酞菁。另外,也可将制得的铜酞菁通过公知的方法进行适当的卤化等的变性。
实施例
以下利用实施例具体说明本发明。(反应溶剂的制造例)
叔丁基二甲苯的制造
将由邻、间、对二甲苯组成的混合二甲苯530g与3g无水氯化铝加入到带有搅拌机的反应容器内,冰冷保持温度在10℃以下,同时在常压下将280g异丁烯直接注入反应液内,使反应。通过减压过滤从得到的反应混合物中除去催化剂,然后在50mmHg的减压下得到馏出温度为120-128℃的馏分763g(收率94.1%)。
该馏分通过质谱、1H、13C-NMR分析结果可确认是由3种叔丁基化的二甲苯(以叔丁基邻二甲苯为主,此外还含有叔丁基间二甲苯及叔丁基对二甲苯)组成的混合物。
将其作为反应溶剂1。
在以下的实施例及比较例中,使用下述的反应溶剂。另外,反应溶剂1以外的为特级试剂。反应溶剂1:上述制造例的溶剂反应溶剂2:异丙基二甲苯反应溶剂3:仲丁基二甲苯反应溶剂4:叔丁基苯〔铜酞菁的制造〕
将苯二酸酐21.0g、尿素23.0g、无水氯化亚铜3.6g、钼酸铵0.007g与100g反应溶剂1-4分别供给带有回流冷却器、搅拌机、温度计及加热器的300ml的四口烧瓶中,保持在180-185℃范围内的任意温度,使反应2小时。在使用反应溶剂4的情况下该反应温度为回流温度。无论使用何种溶剂,因为带有回流冷却器,所以可与大气相通,在进行反应期间蒸发出来的大量反应溶剂蒸汽可通过回流冷却器冷凝、回流,在冷却器中为与空气相接触的状态。
反应后,在反应物冷却后,通过减压过滤进行回收,以400g的甲醇洗2次,过滤。除去溶剂后,在2%的氢氧化钠水溶液4升中煮沸洗净1小时,过滤后反复用热水洗净直至洗净水达到中性。再用2%盐酸2升与上述相同进行煮沸洗净、过滤、热水洗净至中性,得到蓝色粉末的铜酞菁颜料。在温度为85-95℃的减压干燥器内干燥后,将得到的颜料用于下述的鲜明度试验。
将得到的颜料12g、椰子油变性醇酸树脂(含油率33%的二甲苯的60%溶液)56g、三聚氰胺树脂、二甲苯10g加入到容量为300ml的陶制旋转式球磨机内,混练5小时,调制成颜料分散涂料。
将制得的涂料在厚度为0.2mm的白色上等纸上用膜厚为10密耳(ミル)的给液器涂布后,在120℃下进行热风干燥烧制,测定涂料涂布面的反射率及涂布面的色相的浓度。反射率的测定使用610nm的波长,以上等白纸的反射率作为100%基准。
颜料的收率、鲜明度试验的结果等如表1所示。
表1
*:表示涂布面的色相的浓度,该数值越小表示颜料的鲜明度越高。
反应溶剂 | 颜料的收率(gr) | 涂布面的浓度* |
1 | 19.7 | 4.6 |
2 | 16.8 | 4.9 |
3 | 19.6 | 6.7 |
4 | 13.3 | 8.2 |
使用本发明的带有具有特定构造的支链型C4侧链的烷基二甲苯类,在制造铜酞菁颜料时,不必对装置特别加压即可确保反应温度,在装置上不必设置特别的附带设备。另外,因为没有必要在高温加压下处理大量的可燃性物质,所以容易确保安全性。
另外,本发明的带有具有特定构造的支链型C4侧链的烷基二甲苯类,与具有其他的骨架构造的溶剂例如异丙基二甲苯、仲丁基二甲苯、叔丁基苯、叔戊基苯等相比,制得的颜料色调鲜明,且相对于加入的原料制得的颜料的收率提高,作为实用溶剂优选。
Claims (1)
1.铜酞菁颜料的制造方法,其特征在于,将苯二酸酐或其衍生物与尿素及含铜物质、或酞腈或其衍生物与含铜物质在反应溶剂中进行加热反应制造铜酞菁颜料的方法中,使用以下式(1)表示的带有支链型C4侧链的烷基二甲苯成分作为该反应溶剂。
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KR100731881B1 (ko) * | 2001-01-18 | 2007-06-25 | 엘지전자 주식회사 | 지하철 최단노선과 도착시간 정보를 안내하는 방법 및시스템 |
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