CN1309789C - 双偶氮染料的铜络合物用于使天然与合成材料染色的应用 - Google Patents
双偶氮染料的铜络合物用于使天然与合成材料染色的应用 Download PDFInfo
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- 238000004043 dyeing Methods 0.000 title claims abstract description 10
- 229920002994 synthetic fiber Polymers 0.000 title claims abstract description 6
- 239000000975 dye Substances 0.000 title claims description 37
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title description 2
- 150000001879 copper Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004699 copper complex Chemical class 0.000 claims description 32
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 claims description 18
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- -1 4Be hydrogen Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004040 coloring Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
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- 239000003352 sequestering agent Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims 2
- 239000002253 acid Substances 0.000 description 53
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- IUBANARRFVKYIF-UHFFFAOYSA-N 4-ethyl-1,3,5-triazin-2-amine Chemical compound CCC1=NC=NC(N)=N1 IUBANARRFVKYIF-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- 238000009472 formulation Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TZBROGJRQUABOK-UHFFFAOYSA-N 4-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 TZBROGJRQUABOK-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010014 continuous dyeing Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- CDVLCTOFEIEUDH-UHFFFAOYSA-K tetrasodium;phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O CDVLCTOFEIEUDH-UHFFFAOYSA-K 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/28—Disazo or polyazo compounds containing copper
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/919—Paper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Paper (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
以下分子式的染料的单铜络合物以及其与该染料的双铜络合物的混合物用于使天然与合成材料染色的应用:其中Z1,Z2,R1,R2,R3,R4,X,n和m见权利要求中的定义。
Description
本发明涉及以下分子式的染料的单铜络合物的应用,和涉及这一单铜络合物与该染料的双铜络合物的混合物的应用,其用于使天然与合成材料染色,其中该混合物含有最多达50wt%的双铜络合物:
其中
Z1和Z2彼此独立地为氢原子、羟基、烷氧基或基团-NHR5,
R5是氢、烷基、芳基、-COR6、-CO-NHR6、-SO2R6或-COOR6,
R6是氢、烷基或芳基,
R1和R3彼此独立地为羟基或烷氧基,或这些基团之一也可以是烷基,
R2和R4彼此独立地为氢原子、羟基、烷基或烷氧基、卤素、磺基、羧基、-NHCONHR6或-NHCOR6,
X为桥连部份(bridging member),但不是直接的化学键,
n和m彼此独立地为1或2,
在萘基中的OH基处在偶氮基团的邻位,
和其中环A和B可彼此独立地带有稠合的苯环。
R7和R8彼此独立地为氢原子、未被取代或被取代的烷基、或未被取代或被取代的芳基。
在本申请中,卤素通常为氟、溴或特别是氯。
根据本发明,烷基应理解为通常开链或支链或环状的烷基,优选含有1-8个碳原子,例如甲基、乙基、正丙基或异丙基、正丁基、仲丁基或叔丁基、正己基、正辛基、环戊基和环己基。
芳基应理解为特别是萘基或苯基,特别是未被取代的萘基或苯基。
这些烷基以及环烷基或芳基可以例如被羟基、羧基、卤素、氰基、氨基或C1-C4烷氧基单-或多-取代。
烷氧基可具有1-12个碳原子,优选1-4个碳原子,和是例如甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基或叔丁氧基、正戊氧基和正己氧基。烷氧基也可例如被可作为烷基取代基列举的基团取代,特别是被羟基或C1-C4烷氧基取代。
在分子式(1)的染料中和在铜络合物中,Z1和Z2优选氢、羟基、烷氧基、氨基或苯胺基,其未被取代或被氨基和/或磺基取代。
R2和R4优选氢、C1-C4烷基或C1-C4烷氧基,
在本申请中,以游离酸形式表示染料,但也包括相应的盐,例如金属盐或铵盐,例如烷基-或羟烷基铵盐。
在单铜和双铜络合物的混合物中,络合物赖以为基础的染料优选相同。
优选的混合物含有1-35wt%,优选5-25wt%的双铜络合物。
以本身已知的方式,通过用产铜剂(copper-yielding agent)对常规制备的分子式(1)的染料进行铜-处理,获得单铜络合物及其与双铜络合物的混合物,其中产铜剂的用量为1-1.5mol铜/mol分子式(1)的染料。也可通过裂解烷氧基导致脱甲基化进行铜-处理,或引入额外的含氧基团氧化地进行铜-处理。
取决于桥连部分X的本性,通过X连接的分子式(1)的染料的两部分之一也可与最多达1mol产铜剂反应,然后借助桥连部分X连接到未进行-铜-处理的第二部分上。然而,优选由分子式(1)的染料起始并使染料与产铜剂反应。
可使用单铜络合物或使用单铜络合物与双铜络合物的混合物染色的天然与合成材料例如是皮革的纤维材料、羊毛、聚酰胺、玻璃纤维或棉,和特别是纸。
使用常规的染色方法,在这种材料上获得具有良好坚牢度性能,特别是良好耐光度性能的蓝色染色。可通过所使用的铜量控制色调和耐光度。可将来自合成的流出液中的游离铜量降低到100ppm之下的值,同时仍然获得良好的耐光度性能。
分子式(1)的染料已属公知,同样公知的是其双铜络合物在使纤维素材料染色时用于改进耐光度的应用。但是,在双铜络合物的常规合成中,流出物中含有显著量的铜,只能以复杂的方法去除。
优选以固体或液体的商业形式使用单铜络合物或其与双铜络合物的混合物。
在粉剂或颗粒形式中,特别地以间歇本体染色法(mass dyeing)使用染料混合物,其中将通常以贮液形式的染料混合物加入到碎浆机、打浆机或混合瓮中。在此情况下,优选使用染料制剂,该染料制剂除了包括染料混合物之外,还可包括稀释剂例如作为加溶剂的脲、糊精、芒硝、氯化钠和分散剂、隔离剂(dusting agent)和螯合剂如磷酸四钠。
因此本发明还涉及使纸张染色用的固体染料制剂,该制剂包括本发明使用的单铜络合物或其与相应的双铜络合物的混合物和进一步的添加剂。
近年来,染料的浓缩水溶液的应用的重要性增加,特别地由于这种溶液比粉剂形式的染料具有的优点。通过使用溶液,避免了与粉剂的形成有关的难度且用户免于耗时和通常困难的将染料粉剂溶解在水中的过程。此外,通过纸张用的连续染色工艺的开发,已促进了浓溶液的应用,因为在那些工艺中有利地向纸浆流中直接地或在造纸过程中的任何其它合适的位置处加入计量用量的溶液。
因此本发明还涉及使纸张染色用的在本发明中使用的单铜络合物的浓缩水溶液或其与双铜络合物的混合物的浓缩水溶液,该溶液含有5-30wt%的铜络合物,基于溶液的总重量。
浓溶液可包括进一步的助剂,例如加溶剂,如ε-己内酰胺或脲、有机溶剂如二元醇、聚乙二醇、二甲亚砜、N-甲基吡咯烷酮、乙酰胺、链烷醇胺或聚乙二醇胺。
下述实施例用于阐述本发明,但不将本发明限制至此。份数和百分数均指重量而言,除非另有定义。
实施例1:
将18.4份(0.02mol)分子式(A)的染料溶解在170份水和7份25%的氢氧化铵中,并在100℃下与5份(0.02mol)CuSO4·5H2O一起搅拌直到反应完全。
在5小时的反应时间之后,通过极谱法进行游离铜的分析试验,表明<20ppm的值。反应溶液包括与相应的双铜染料(Direct Blue 290)混合的分子式(B)的染料。
所得反应混合物使纤维素纤维,和特别是纸张染色成亮光的微红-蓝色色调,其具有良好的坚牢度性能和具有高的上染率。在纸张上的染色耐光度几乎与单独使用Direct Blue 290的相应染色一样地好。
粗的反应溶液在没有中间分离的情况下,可进一步直接加工成液体制剂。在文献中所述的常规方法,特别是膜技术可用于此目的,任选地使用此前所述的钠盐之外的盐形式,并加入改进溶解性用的常规水溶助长剂。
当使用0.03mol或0.01mol硫酸铜,而不是0.02mol硫酸铜时,类似地获得有价值的染料混合物。
实施例2-25:
通过如实施例1中所述的顺序,但使用具有与实施例1所示的结构(A)相类似的染料,获得与实施例1所示的结构(B)相类似的含新型蓝色单铜络合物的进一步的混合物,与结构(A)相似的染料通过在下表的第二栏中所列举的二胺的四氮化作用(tetraazotisation)并偶合到第三栏中所列举的偶联组分上而获得的。
实施例 | 二胺 | 偶联组分 |
2345678910111213 | 4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯 | 1,8-二羟基萘-3,6-二磺酸1-萘醇-3,6-二磺酸1-萘醇-3,8-二磺酸1-萘醇-4,8-二磺酸2-萘醇-3,6-二磺酸2-萘醇-5.7-二磺酸2-萘醇-6,8-二磺酸1-萘醇-5-磺酸2-萘醇-6-磺酸1-氨基-8-萘醇-3,6-二磺酸1-氨基-8-萘醇-2,4-二磺酸1-氨基-8-萘醇-4,6-二磺酸 |
141516171819202122232425 | 4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯4,4`-二氨基-3,3`-二甲氧基氧化偶氮苯 | 2-氨基-5-萘醇-1,7-二磺酸3-氨基-5-萘醇-2,7-二磺酸2-氨基-5-萘醇-7-磺酸3-氨基-5-萘醇-7-磺酸2-氨基-5-萘醇-4,8-二磺酸2-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸3-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸1-乙氧基羰基氨基-8-萘醇-3,6-二磺酸1-对甲苯基磺酰基氨基-8-萘醇-3,6-二磺酸1-脲基-8-萘醇-3,6-二磺酸2-(3-磺基苯胺基)-5-萘醇磺酸1-萘醇-3,6-二磺酸和1-乙氧基羰基-8-萘醇-3,6-二磺酸(1∶1) |
实施例26-69:
通过如实施例1中所述的顺序,但使用具有与实施例1所示的结构(A)相类似的染料,获得与实施例1所示的结构(B)相类似的含新型蓝色单铜络合物的进一步的混合物,与结构(A)类似的染料通过在下表的第二栏中所列举的二胺的四氮化作用,并偶合到第三栏中所列举的偶联组分上而获得的。
实施例 | 二胺 | 偶联组分 |
262728293031323334353637383940 | 4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯 | 1-羟基萘-3,6-二磺酸1,8-二羟基萘-3,6-二磺酸1-萘醇-3,6-二磺酸1-萘醇-3,8-二磺酸1-萘醇-4,8-二磺酸2-萘醇-3,6-二磺酸2-萘醇-5,7-二磺酸2-萘醇-6,8-二磺酸1-萘醇-5-磺酸2-萘醇-6-磺酸1-氨基-8-萘醇-3,6-二磺酸1-氨基-8-萘醇-2,4-二磺酸1-氨基-8-萘醇-4,6-二磺酸2-氨基-5-萘醇-1,7-二磺酸3-氨基-5-萘醇-2,7-二磺酸 |
414243444546474849505152535455 | 4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基偶氮苯4,4`-二氨基-3,3`-二甲氧基二苯基脲4,4`-二氨基-3,3`-二甲氧基二苯基脲4,4`-二氨基-3,3`-二甲氧基二苯基脲4,4`-二氨基-3,3`-二甲氧基二苯基脲4,4`-二氨基-3,3`-二甲氧基二苯基脲4,4`-二氨基-3,3`-二甲氧基二苯基脲 | 2-氨基-5-萘醇-7-磺酸3-氨基-5-萘醇-7-磺酸2-氨基-5-萘醇-4,8-二磺酸2-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸3-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸1-乙氧基羰基氨基-8-萘醇-3,6-二磺酸1-对甲苯基磺酰基氨基-8-萘醇-3,6-二磺酸1-脲基-8-萘醇-3,6-二磺酸2-(3-磺基苯胺基)-5-萘醇磺酸1-萘醇-3,6-二磺酸和1-乙氧基羰基-8-萘醇-3,6-二磺酸(1∶1)1-羟基萘-3,6-二磺酸1,8-二羟基萘-3,6-二磺酸1-氨基-8-萘醇-3,6-二磺酸2-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸1-乙氧基羰基氨基-8-萘醇-3,6-二磺酸 |
5657585960616263646566676869 | 4,4`-二氨基-3,3`-二甲氧基二苯基脲4,4`-二氨基-3,3`-二甲氧基二苯基脲1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪1,3-二(3`-甲氧基-4`-氨基)-2-二羟基乙基氨基-2,4,6-三嗪4,4`-二氨基-二苯基胺4,4`-二氨基-二苯基胺4,4`-二氨基-二苯基胺4,4`-二氨基-二苯基胺 | 1-对甲苯基磺酰基氨基-8-萘醇-3,6-二磺酸1-脲基-8-萘醇-3,6-二磺酸1-羟基萘-3,6-二磺酸1,8-二羟基萘-3,6-二磺酸1-氨基-8-萘醇-3,6-二磺酸2-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸1-乙氧基羰基氨基-8-萘醇-3,6-二磺酸1-对甲苯基磺酰基氨基-8-萘醇-3,6-二磺酸1-脲基-8-萘醇-3,6-二磺酸1,8-二羟基萘-3,6-二磺酸1-萘醇-3,6-二磺酸1-氨基-8-萘醇-3,6-二磺酸1-苯甲酰基氨基-8-萘醇-3,6-二磺酸2-(4-氨基-3-磺基苯胺基)-5-萘醇-7-磺酸 |
Claims (10)
1.一种下式(1)的染料的单铜络合物的应用,或这一单铜络合物与该染料的双铜络合物的混合物的应用,用于使天然与合成材料染色,其中该混合物含有最多达50wt%的双铜络合物:
其中
Z1和Z2彼此独立地为氢原子、羟基、C1-12烷氧基、未被取代或被氨基和/或磺基取代的苯胺基、或基团-NHR5,
R5是氢、开链或支链或环状的C1-8烷基、-CO-NHR6、-SO2R6或-COOR6,
R6是氢、开链或支链或环状的C1-8烷基或芳基,
R1和R3彼此独立地为羟基或C1-12烷氧基,或这些基团之一也可以是开链或支链或环状的C1-8烷基,
R2和R4彼此独立地为氢原子、羟基、开链或支链或环状的C1-8烷基或C1-12烷氧基、卤素、磺基、羧基、-NHCONHR6或-NHCOR6,
X是选自偶氮基、氧化偶氮基、-C=C-、
C1-C4烷氧基或-NR7R8,R7和R8彼此独立地为氢原子、开链或支链或环状的C1-8烷基或芳基,
n和m彼此独立地为1或2,
在萘基中的OH基处在偶氮基团的邻位,和
其中环A和B可彼此独立地带有稠合的苯环,和所述烷基、环烷基、烷氧基或芳基可以被羟基、羧基、卤素、氰基、氨基或C1-C4烷氧基单-或多-取代。
2.权利要求1的应用,其中Z1和Z2是氢、羟基、C1-12烷氧基、氨基、或未被取代或被氨基和/或磺基取代的苯胺基。
3.权利要求1或2的应用,其中R2和R4是氢、C1-C4烷基或C1-C4烷氧基。
4.权利要求1或2的应用,其中在单铜和双铜络合物的混合物中,络合物赖以为基础的染料是相同的。
5.权利要求1或2的混合物的应用,其中含有1-35wt%的双铜络合物。
6.一种使纸张染色用的固体染料制剂,该制剂包括权利要求1中分子式(1)的单铜络合物或其与相应的双铜络合物的混合物和进一步的添加剂。
7.权利要求6的固体染料制剂,其包括稀释剂、加溶剂、分散剂、隔离剂或螯合剂作为进一步的添加剂。
8.一种使纸张染色用的浓缩水溶液,该溶液包括权利要求1中分子式(1)的单铜络合物或其与相应的双铜络合物的混合物和任选地进一步的添加剂。
9.权利要求8的浓缩水溶液,包括加溶剂或有机溶剂作为助剂。
10.一种纸张,它是使用权利要求1中分子式(1)的单铜络合物或其与相应的双铜络合物的混合物或使用权利要求6的固体染料制剂或权利要求8的浓缩水溶液染色的。
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- 2001-12-19 BR BR0116601-8A patent/BR0116601A/pt not_active IP Right Cessation
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- 2001-12-19 ES ES01272650T patent/ES2259009T3/es not_active Expired - Lifetime
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- 2001-12-19 AU AU2002219203A patent/AU2002219203B2/en not_active Ceased
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FR1161475A (fr) * | 1956-09-18 | 1958-09-01 | Gen Aniline & Film Corp | Colorant disazoïque contenant du cuivre |
US3399187A (en) * | 1964-09-30 | 1968-08-27 | Geigy Ag J R | Copper-containing disazo dyestuffs |
DE2138791A1 (de) * | 1970-08-05 | 1972-02-10 | Sandoz Ag, Basel (Schweiz) | Papierfarbstoff |
US4514188A (en) * | 1982-10-26 | 1985-04-30 | Bayer Aktiengesellschaft | Use of disazo-copper complex dyestuffs for dyeing natural and synthetic materials |
WO2000055259A1 (de) * | 1999-03-13 | 2000-09-21 | Basf Aktiengesellschaft | Azoxyfarbstoffe und deren cu-komplexe |
Also Published As
Publication number | Publication date |
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EP1345993A2 (en) | 2003-09-24 |
US20040054153A1 (en) | 2004-03-18 |
JP2004517228A (ja) | 2004-06-10 |
KR100847235B1 (ko) | 2008-07-18 |
KR20030064875A (ko) | 2003-08-02 |
DE60117702D1 (de) | 2006-05-04 |
MXPA03004829A (es) | 2003-08-19 |
AU2002219203B2 (en) | 2006-08-24 |
BR0116601A (pt) | 2004-02-10 |
EP1345993B1 (en) | 2006-03-08 |
WO2002053650A2 (en) | 2002-07-11 |
DE60117702T2 (de) | 2006-11-16 |
CN1483064A (zh) | 2004-03-17 |
ES2259009T3 (es) | 2006-09-16 |
WO2002053650A3 (en) | 2002-09-26 |
US6984723B2 (en) | 2006-01-10 |
JP4141837B2 (ja) | 2008-08-27 |
CA2429487A1 (en) | 2002-07-11 |
ATE319783T1 (de) | 2006-03-15 |
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