CN1916082A - Novel quinonimine sulfur dye compositions, methods for producing them and their use for dyeing cellulose-containing material - Google Patents
Novel quinonimine sulfur dye compositions, methods for producing them and their use for dyeing cellulose-containing material Download PDFInfo
- Publication number
- CN1916082A CN1916082A CNA2005100927530A CN200510092753A CN1916082A CN 1916082 A CN1916082 A CN 1916082A CN A2005100927530 A CNA2005100927530 A CN A2005100927530A CN 200510092753 A CN200510092753 A CN 200510092753A CN 1916082 A CN1916082 A CN 1916082A
- Authority
- CN
- China
- Prior art keywords
- colourless
- dye composition
- sulfur dye
- sulfur
- preparation
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000004043 dyeing Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 16
- 229920002678 cellulose Polymers 0.000 title claims abstract description 9
- 239000001913 cellulose Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 45
- 239000000988 sulfur dye Substances 0.000 title claims description 32
- 239000000975 dye Substances 0.000 claims description 101
- 238000002360 preparation method Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 29
- 230000002829 reductive effect Effects 0.000 claims description 25
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 claims description 24
- 238000005868 electrolysis reaction Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- FMKXFJQAVQXMPX-UHFFFAOYSA-N 4-(9h-carbazol-3-ylimino)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=NC1=CC=C(NC=2C3=CC=CC=2)C3=C1 FMKXFJQAVQXMPX-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- -1 piperazine ketone Chemical class 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005885 Buprofezin Substances 0.000 claims description 4
- PRLVTUNWOQKEAI-VKAVYKQESA-N buprofezin Chemical compound O=C1N(C(C)C)\C(=N\C(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-VKAVYKQESA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000003637 basic solution Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 235000011121 sodium hydroxide Nutrition 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XAWPKHNOFIWWNZ-UHFFFAOYSA-N 1h-indol-6-ol Chemical compound OC1=CC=C2C=CNC2=C1 XAWPKHNOFIWWNZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920001732 Lignosulfonate 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- QAYICIQNSGETAS-UHFFFAOYSA-N dazomet Chemical compound CN1CSC(=S)N(C)C1 QAYICIQNSGETAS-UHFFFAOYSA-N 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000002895 hyperchromatic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- 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
-
- 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
- C09B67/0078—Preparations of vat, sulfur or indigo dyes in liquid form
-
- 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
- C09B49/00—Sulfur dyes
-
- 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Paper (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to novel leuko-sulfuric dye compositions which are characterized in that they are accessible at current densities between 50 mA/cm<2> and 500 mA/cm<2> and a velocity of flow of 0.1 m/s to 2 m/s, preferably at 0.1 to 0.4 m/s. The invention also relates to the production of these dye compositions and to their use for dyeing cellulose-containing material.
Description
Technical field
The present invention relates to the novel colourless sulfur dye composition of quinonimine thioxine dyes class, the invention still further relates to the method for preparing this colourless sulfur dye composition by electrochemical reduction, this method is undertaken by the controlled change of used multiple electro-chemical machining condition.
Background technology
The quinonimine thioxine dyes comprises the dye class of reacting formation by for example polynitration phenol (polynitrated phenol), halogeno-benzene, indolol or indoaniline and sulphur, alkali metalsulphide or alkali metals polysulfide in water or pure medium.This class dyestuff specifically comprises the thioxine dyes of purple, blueness, green, reddish-brown and black.Oligomeric or the polymerisate that obtains contains the organic structure repeating unit (for example phenthiazone, Buprofezin (thiazone), thianthrene and fen _ piperazine ketone minor structure) that links together by disulfide linkage.Reference Angewandte Chemie60 (1948), 141-147 has described these structures.
In order to use these sulfur dyeings, promptly use dyestuff (ready-to-dye) by multiple method of reducing with what they were converted into colorless form, the dyestuff of this form reduces the quinonimine functionality on the one hand, and reductibility ground disconnects disulfide linkage on the other hand.The leucocompound that obtain have lower molar weight usually and comprise the material of wide molecular weight scope.They dissolve in alkaline water medium and can be used in dyeing to cellulose materials.
At suitable oxygenant, under the existence as airborne oxygen, superoxide or bromate, dyestuff is returned so that equation shown below is fully oxidized to some extent, and wherein R represents organic repeated structural unit, for example phenthiazone, Buprofezin, thianthrene or phenol _ piperazine ketone minor structure.
With in actual dying operation process, just be converted into colorless form and promptly use the thioxine dyes of complete oxidation of dyestuff the same by adding the organic or inorganic reductive agent, promptly also having with the colourless thioxine dyes kind of dyestuff pre-reduction type that degree is different is commercially available, for example Cassulfon_Carbon CMR.Preferred these dyestuffs are prepared with big technical scale by being added in inorganic or organic reducing agent in the alkaline medium such as Sodium sulfhydrate or glucose.
The shortcoming of these existing methods is, owing to used reductive agent exists very high refuse concentration and salt load and causes high COD, TOC in the waste water of dyehouse to load.These by products can only drop into a large amount of engineerings and be removed in the upstream in wastewater treatment stage by expensive, loaded down with trivial details method such as membrane technique.
Known a kind of alternative, eco-friendly method of reducing from DE 1906083 and EP 10122210 documents for example.DE 1906083 recommends to pass through in the aqueous solution with 5mA/cm
2To 50mA/cm
2Current density make reducing dyes by cathodic reduction.Yet this method is inapplicable in the situation of commercially available pre-reduction type thioxine dyes, and commercially available pre-reduction type thioxine dyes is mixed with other stable reductive agent usually in dye solution, because acutely emit hydrogen in reduction process.EP 1012210 patent specifications have been described at 0.5mA/cm
2To 5mA/cm
2Current density under the method for reduction-sulfurization dyestuff.
Summary of the invention
Surprisingly, find to use 50mA/cm now
2To 500mA/cm
2Current density and 0.1m/s might obtain the novel colourless sulfur dye composition that can not prepare by the conventional reduction method of using the organic or inorganic reductive agent to the flow velocity of 0.4m/s.
Therefore, the invention provides can be at 50mA/cm
2To 500mA/cm
2, preferred 50mA/cm
2To 150mA/cm
2Current density and the novel colourless sulfur dye composition that obtains under to 2m/s, preferred 0.1m/s to the flow velocity of 0.4m/s of 0.1m/s.
The method that is used to prepare colourless sulfur dye composition of the present invention is new, and it forms the part of theme of the present invention equally.Emit for fear of the hydrogen under this high current density, electrochemical reduction carries out under quite high dye strength, at concentration and the 0.5mA/cm of 80g/l
2Initial current density under begin, and increase continuously concentration to 500g/l with increase continuously current density to 500mA/cm
2Method of the present invention might make dye strength be reduced to 500g/l.
Colourless sulfur dye composition of the present invention prepares in alkaline medium, preferred pH＞9.5.Preferred use an alkali metal salt particularly the basic solution of sodium hydroxide, potassium hydroxide or yellow soda ash as conducting electrolyte.Especially preferably use the sodium hydroxide dilute aqueous soln.The concentration of the conducting salt that adds be 0.1mol/l to 5mol/l, be preferably 0.1mol/l to 1.5mol/l.
The Bunte salt of following general formula that perhaps, can be by adding catalytic amount prevents that hydrogen from emitting:
R-S-SO
3Na，
Wherein R represents organic repeated structural unit, and its example is phenthiazone, Buprofezin, thianthrene or phenol _ piperazine ketone minor structure; Or the chemical reducing agent by adding catalytic amount for example V-Brite B, organic-sulfinic acid and/or organic sugar prevent that hydrogen from emitting, the amount of making can be at most 5 weight % of the initial consumption of the thioxine dyes that will be reduced.In addition, after adding Bunte salt or reductive agent, from 80g/l and 0.5mA/cm
2Initial current density begin, concentration increases continuously 500g/l.
Basically all isolated forms lead directly to pond (divided flowthrough cell) and all are applicable to preparation colourless sulfur dye composition of the present invention.The negative electrode that uses not only can be the large flat electrode, and can be three-dimensional negative electrode.
Preferably 20 ℃ to 135 ℃, more preferably at 20 ℃ to 95 ℃ following preparation colourless sulfur dye compositions of the present invention.
If desired, can reduce in the presence of commercially available wetting agent, its example is sulfonated lignin.
Preferred method reduction C.I.Leuco Sulfur Black 1 of the present invention or the C.I.VatBlue 43 of using.In principle, the mixture of different thioxine dyess also can be by method reduction of the present invention.
In the present invention reduced the situation of C.I.Leuco Sulfur Black 1, the concentration of the reducing equivalent of record was that 150Ah/kg is to 534Ah/kg with respect to 1kg drying solid dyestuff.
In the present invention reduced the situation of C.I.Vat Blue 43, the concentration of the reducing equivalent of record was that 75Ah/kg is to 225Ah/kg with respect to 1kg drying solid dyestuff.
Use common HPLC technology and for example material described in the document DE 10 120 821 to measure the composition of each colourless thioxine dyes mixture.
Table 1 expression, compare to 3 with the sample 1 of electrochemical reduction under different current densities, the HPLC spectral results of the C.I.Sulfur Black 1 of reversion, sample 1 reduces by method of the present invention, sample 2 is by the reduction of the method described in the document DE 1906083, and sample 3 is by the reduction of the method described in the EP 10122210.
The composition of the C.I.Sulfur Black 1 that table 1:HPLC measures
| Dyestuff 1 retention time (area %) | Dyestuff 2 retention time (area %) | Dyestuff 3 retention time (area %) | Dyestuff 4 retention time (area %) | | |
| Sample 1 (Fig. 1) (j=100mA/cm 2) | Minute 2.8 (31.7) | Minute 3.0 (65.5) | |||
| Sample 2 (Fig. 2) (j=20mA/cm 2) | Minute 1.6 (5.0) | Minute 2.5 (13.5) | Minute 2.9 (81.3) | ||
| Sample 3 (Fig. 3) (j=0.48mA/cm 2) | Minute 1.6 (10.9) | Minute 2.5 (18.7) | Minute 2.9 (69.6) | ||
| Sample 4 (Fig. 4) (0.8mA/cm 2＜j＜101 mA/cm 2) | Minute 2.6 (1.16) | Minute 2.8 (43.72) | Minute 3.0 (53.8) | ||
| C.I.Sulfur Black 1 (sulfide-reduction) (Fig. 5) | Minute 1.6 (1.7) | Minute 2.0 (4.2) | Minute 2.5 (4.9) | Minute 2.9 (30.5) | Minute 3.0 (58.3) |
Surprisingly, general＞50mA/cm
2High current density be used in combination with the high flow rate that allows dyestuff to the optimal transport of electrode, make C.I.Sulfur Black 1 have narrower species distribution, thus the narrower molecular distribution of generation.
Table 2 expression is compared with the sample 6 to 7 of electrochemical reduction under different current densities, the HPLC spectral results of the C.I.Vat Blue 43 of reversion, and sample 6 reduces by method of the present invention, and sample 7 reduces according to method described in the document EP 10122210.
| Dyestuff 1 retention time (area %) | Dyestuff 2 retention time (area %) | Dyestuff 3 retention time (area %) | Dyestuff 4 retention time (area %) | | |
| Sample 6 (Fig. 6) (j=100mA/cm 2) | Minute 4.21 (6.07) | Minute 6.03 (13.18) | Minute 6.97 (50.91) | Minute 9.77 (12.61) | Minute 14.89 (6.99) |
| Sample 7 (Fig. 7) (j=10mA/cm 2) | Minute 3.62 (4.26) | - | Minute 7.92 (52.25) | Minute 10.99 (35.07) | Minute 16.53 (6.80) |
| C.I.Vat Blue 43 (sulfide-reduction) (Fig. 8) | Minute 5.15 (49.28) | Minute 6.10 (11.06) | Minute 6.45 (12.95) | Minute 7.10 (16.01) | Minute 10.65 (7.56) |
Colourless thioxine dyes solution of the present invention not only can be applied to fiber by the classical dyeing process that uses excessive greatly Sodium sulfhydrate (NaHS), and can be applied to fiber under shielding gas described in the DE of Offenlegungsschriff 10234825 A1 or the electrochemical conditions under the dyeing of the best is formed.Reductive condition only is used for compensating the atmosphericoxygen that is introduced in staining fluid.This makes might obtain wherein salt, COD and the low waste water of TOC content.Therefore, the application of colourless sulfur dye composition of the present invention provides ecological benefit and economics benefit in essence.
Perhaps, also might want the direct dye composite of the present invention that in dye bath, prepares by the electrochemical reduction preparation.
Carry out electrolysis at the titanium electrode of for example wherein being separated and being contained stainless steel cathode by cationic exchange membrane and scribble the stainless steel mixed oxide in as the anodic pond, electrolysis is in the presence of electroconductibility electrolysis liquid, at 50mA/cm
2To 500mA/cm
2, preferred 50mA/cm
2To 150mA/cm
2Current density under and 0.1m/s to 2m/s, preferably 0.1m/s carries out under the flow velocity of 0.4m/s, dye bath cycle through the material that will be colored and as the pumping of sewage discharging current by the cathodic area, make dye bath continue to regenerate by exchanging with catholyte.Catholyte contains the thioxine dyes that will be reduced, for example C.I.Sulfur Black 1 or C.I.Vat Blue 43, if desired, also contain wetting agent, conducting electrolyte (preferred as alkali salt is the basic solution of sodium hydroxide, potassium hydroxide or yellow soda ash particularly, more preferably the dilute aqueous soln of sodium hydroxide) and conducting salt.The concentration of the conducting salt that adds be 0.1mol/l to 5mol/l, be preferably 0.1mol/l to 1.5mol/l.
Being ready for painted cellulose materials is in the dye bath.
Dyeing procedure comprises a plurality of stages:
Reduction and heating phase
Dyeing and cooling stages
Thioxine dyes oxidation, rinsing and drying are finished dyeing.
The painted color evaluation of using colourless thioxine dyes of the present invention to obtain shows, compare with the colourless thioxine dyes for preparing by use chemical reducing agent routine, their notable feature is to have significantly lower waste part, and these waste parts do not have avidity to fiber.This causes form and aspect purer, and the form and aspect drift of the colourless sulfuration dyeing composition of simultaneous electrochemistry generation.Observe C.I.Sulfur Black 1 experience significantly to more blue, redder, cleaner form and aspect drift.These effects of same observed C.I.Vat Blue 43 just need in addition necessary change.
Look trajectory measurement method (color locus) colorimetric evaluation dyeing by DIN 6174 and DIN 5033.
Shown in the L value in the table 3, the electrochemical reduction of dyestuff the method according to this invention under the current density that increases of low amount obtains same colour strength.
Table 3:
| Think that exsiccant reoxidizes dyestuff/kilogram solution | L (brightness) | A (red-green) | B (Huang-indigo plant) | |
| C.I.Sulfur Black 1 (sulfide-reduction) | 280g | 16.03 | -0.33 | -1.26 |
| Sample 1 (j=100mA/cm 2) | 247.2g | 16.01 | -0.08 | -1.67 |
| Sample 3 (j=0.48mA/cm 2) | 283.2g | 15.68 | -0.16 | -1.53 |
By dip method, the degree of depth of color harmony form and aspect is by the look trajectory measurement method of dyeing (10% sulfuration dyeing), as the function call of dye strength and current density to describe.In the situation of C.I.Vat Blue43, obtained remarkable displacement (redder under higher current density) as the form and aspect of the function of used current density, as shown in table 4.
Table 4:
| L (brightness) | A (red-green) | B (Huang-indigo plant) | |
| C.I.Vat Blue 43 (sulfide-reduction) | 29.30 | 1.94 | -23.39 |
| Sample 4 (j=100mA/cm 2) | 30.31 | 1.24 | -22.36 |
| Sample 5 (j=10mA/cm 2) | 30.05 | 0.99 | -22.10 |
Except the form and aspect aspect, the noticeable place of thioxine dyes of the present invention is that it need lack the thioxine dyes slurry with maximum 10% than the colourless thioxine dyes solution of chemical preparation for obtaining corresponding colour strength, and therefore uses maximum 10% raw material less.
Can separate as solid material by colourless quinonimine sulfur dye composition, make it stable electrochemical reduction of the present invention.
Therefore, the present invention also provide by pH is reduced to≤9 and/or make colourless quinonimine thioxine dyes solution drying behind the electrochemical reduction prepare the method for the reduced form quinonimine thioxine dyes of the present invention of solid form.
A kind of method of the colourless quinonimine thioxine dyes of separate solid of the present invention for make pH be reduced to≤9, this is by adding organic acid, mineral acid in the solution after reduction and carbonic acid gas is realized.In addition, can regulate thioxine dyes solution after the reduction to pH≤9 by adding entry, thereby make dye precipitated.Obtain product of the present invention by filtration and drying subsequently then.In the method, there are not the salt of avidity and organic constituent to be retained in the solution to fiber.Can carry out oxide treatment to the filtrate that obtains, the COD load is significantly reduced.10 weight % of the residual salt content≤total mass of the dried thioxine dyes that so obtains.
The second method of the colourless quinonimine thioxine dyes of separate solid is with the solution finish-drying after the reduction.Can use conventional dehumidification system and device (for example vaporizer) to carry out drying, for example by spraying drying or film drying, and the exsiccant product further can be pulverized and be reached required particle diameter, make after exsiccant, the reduction, alkaline bleach liquor soluble product can be converted into for example bead, powder or form of chips.Also may prepare by mixing with proper assistant.Another kind of possibility is freeze-drying.
The concentration of the reducing equivalent of the dried colourless thioxine dyes that so obtains is with respect to the drying solid dyestuff of 1kg, in the situation of C.I.Leuco Sulfur Black l,, in the situation of C.I.Vat Blue 43, arrive 225Ah/kg for 75Ah/kg for 150Ah/kg arrives 534Ah/kg.When with respect to whole product, during the water content of colourless thioxine dyes≤5 weight %, preferred≤as during 2 weight %, can to think that it is the exsiccant product.
It is the very simple method of the colourless thioxine dyes of the present invention of stable (not adding other sulfide and other auxiliary agent) colourless sulfur dye composition that described method provides form, the very high and sulfur compound not in fact of described colourless sulfur dye composition concentration, and, when when lower pH value is passed through precipitate and separate, it does not contain salt and the organic constituent that fiber is not had avidity, with respect to whole product, its amount≤1 weight %, preferred≤0.5 weight %.The distinguishing feature of the dyestuff of preparation is its stability to atmospheric oxidn.
It is 20 to 600g/L used dyestuff that the colourless thioxine dyes solution that is used to separate product of the present invention contains concentration.
If in case soluble in water and when suitably mixing with alkali, product of the present invention can be used for cellulose materials or leather coloring.Dyeing process that not only can be by routine is done colourless sulfur dye composition be applied to fiber after dissolving of the present invention, and can be by be applied to fiber at the dye component of use the best under the shielding gas or under the electrochemical conditions as DE 10234825 A1 of Offenlegungsschnft described in.Reductive condition only is used for compensating the atmosphericoxygen that is introduced in staining fluid.Therefore the use of colourless sulfur dye composition of the present invention has formed ecology and economics benefit in essence.The chromatic characteristic of this product is equivalent to apply for the chromatic characteristic of sample described in the DE102004040601.4.
Embodiment
Following examples are used to illustrate the present invention.
Preparation embodiment 1 (sample 1)
The aqeous suspension that is used for electrolysis C.I.SulfurBlack 1 cake of press by the straight-through pond of cationic exchange membrane (Nafion 424) separation.Bring into use a small amount of dyestuff, and in electrolytic process, increase gradually.In the 2L water of the Primasol NF of 50% aqueous sodium hydroxide solution that comprises 8mL and 4ml wetting agent, use thinks that the C.I.Sulfur Black 1 of exsiccant 156.9g begins reaction, and increases continuously the C.I.Sulfur Black 1 that thinks the maximum 2271g of exsiccant in the 5.815L cumulative volume.The anolyte that uses is aqueous sodium hydroxide solution (1mol/l).Use 100mA/cm
2Current density and the flow velocity electrolysis of 0.2m/s 3510 minutes, the concentration of confirmable reducing equivalent is 4.2 after the electrolysis, it is equivalent to the quantity of electric charge that every kilogram of dyestuff is 378Ah.So the solution of preparation can be used for painted purpose after need not to add reductive agent in addition or adding minimum reductive agent.
The HPLC spectrum of reaction product is shown among Fig. 1.
Preparation embodiment 2 (sample 2)
Described in DE 1906083, use the straight-through pond of separating with 20mA/cm by cationic exchange membrane (Nafion 424)
2Current density electrolysis C.I.Sulfur Black 1 suspension.
The HPLC spectrum of reaction product is shown among Fig. 2.
Preparation embodiment 3 (sample 3)
Described in DE 101222210, use the straight-through pond of separating with 0.48mA/cm by cationic exchange membrane (Nafion 424)
2Current density electrolysis C.I.Sulfur Black 1 suspension.
The HPLC spectrum of reaction product is shown among Fig. 3.
Preparation embodiment 4 (sample 4)
The aqeous suspension that is used for electrolysis C.I.SulfurBlack 1 cake of press by the straight-through pond of cationic exchange membrane (Nafion_424) separation.The C.I.Sulfur Black 1 that think exsiccant 337g of use in the 4L water of 50% aqueous sodium hydroxide solution that comprises 16mL begins reaction, and think the C.I.Sulfur Black 1 of exsiccant 126g to the 253g aliquot by in 1320 minutes time, adding gradually, in the cumulative volume that reaches at 6.8L, think the C.I.Sulfur Black 1 of exsiccant 1740g.Electrolysis is at 0.83mA/cm
2Current density begin, and along with the increase of leuco dye concentration is 100mA/cm to the maximum
2, flow velocity is 0.2m/s.
The concentration that can determine reducing equivalent after electrolysis is 5.67, the quantity of electric charge that to be equivalent to every kilogram of dyestuff be 504Ah.The solution that so obtains has and the same molecular composition of dye solution for preparing preparation among the embodiment 1.
The HPLC spectrum of reaction product is shown among Fig. 4.
Can following reaction product isolated, it is a solid matter:
Variant 1:
Dye solution is heated to 130 ℃ and kept 12 hours at 130 ℃, up to dried residue occurring.Separated 34g exsiccant black product, it easily and fully is dissolved in the water and can be used for dyeing.
Variant 2:
60 ℃ with 100g leuco dye solution and carbon dioxide mix, up to pH＜9, dyestuff precipitates fully.Under argon gas, leach sedimentary dyestuff also under reduced pressure 80 ℃ of dryings.Separated 22g exsiccant black product, it easily and fully is dissolved in the dilute aqueous soln of sodium hydroxide and can be used for dyeing.
Preparation embodiment 5 (sample 6)
The aqeous suspension that is used for electrolysis C.I.Vat Blue43 cake of press by the straight-through pond of cationic exchange membrane (Nafion 424) separation.Use thinks that in the 3L water of 50% aqueous sodium hydroxide solution that comprises 8mL and 4mLPrimasol NF wetting agent the C.I.Vat Blue 43 of exsiccant 50.0g begins reaction.Be increased to gradually and in the cumulative volume of 4.6L, think exsiccant 400g C.I.VatBlue 43.The anolyte that uses is aqueous sodium hydroxide solution (1mol/l).Use 100mA/cm
2Current density and the flow velocity electrolysis of 0.2m/s 650 minutes, the concentration of confirmable reducing equivalent is 3 after the electrolysis, is equivalent to the quantity of electric charge that every kilogram of dyestuff is 221.5Ah.So the solution of preparation can be used for painted purpose after need not to add reductive agent in addition or adding minimum reductive agent.
The HPLC spectrum of reaction product is shown among Fig. 6.
Can following reaction product isolated, it is a solid matter:
60 ℃ with 100g dye solution and carbon dioxide mix, up to pH＜9, dyestuff precipitates fully.Under argon gas, leach sedimentary dyestuff also under reduced pressure 80 ℃ of dryings.Separated 15g exsiccant mazarine product, it easily and fully is dissolved in the dilute aqueous soln of sodium hydroxide and can be used for dyeing.
Preparation embodiment 6 (sample 7)
Described in DE 101222104, the straight-through pond of using cationic exchange membrane (Nafion 424) separation is with 10mA/cm
2Current density electrolysis C.I.Vat Blue 43 suspension.
The HPLC spectrum of reaction product is shown among Fig. 7.
Preparation embodiment 7
With dye strength is that 100g Leuco Sulfur Black 1 solution (this solution is according to preparation embodiment 4 preparations of DE 102004040601.4 application) of 330g/L is heated to 130 ℃ and kept 12 hours at 130 ℃, up to dried residue occurring.The dry black product that has separated 34g, it easily and fully is dissolved in the water and can be used for dyeing.
Preparation embodiment 8:
60 ℃ make according to preparation embodiment 4 preparations of DE 102004040601.4 application, dye strength be 100g Leuco Sulfur Black 1 solution of 330g/L and carbon dioxide mix up to pH＜9, dyestuff precipitates fully.Under argon gas, leach sedimentary dyestuff also under reduced pressure 80 ℃ of dryings.Separated the dry black product of 22g, it easily and fully is dissolved in the dilute aqueous soln of sodium hydroxide, and can be used for dyeing.
Preparation embodiment 9:
60 ℃ make according to preparation embodiment 5 preparations of DE 102004040601.4 application, dye strength after being the 100g reduction of 250g/L C.I.Vat Black 43 solution and carbon dioxide mix up to pH＜9, dyestuff precipitates fully.Under argon gas, leach sedimentary dyestuff also under reduced pressure 80 ℃ of dryings.Separated 15g exsiccant mazarine product, it easily and fully is dissolved in the dilute aqueous soln of sodium hydroxide, and can be used for dyeing.
Dyeing
Dip method dyeing with routine
Total amount is 100ml, comprise leuco dye solution according to the C.I.Vat Blue 43 of 16% C.I.SulfurBlack 1 of preparation embodiment 1-5 preparation or l0%, the 2g/l anionic wetting agent, 38 ° of Be caustic soda of 2mI/I, 10ml/l sulfhydrate F 150%, the StabilisalS liq. of 5ml/l, the staining fluid of the sodium sulfate of 30g/l and the complete deionized water of about 50ml, being used in bath raio is that 10: 1 dip-dye method bleaching cotton fabric is as forming the knitted cotton fabric of looped pile, starting temperature at 50 ℃ begins, be heated to 95 ℃ with 2 ℃/minute, then 95 ℃ of dyeing 45 minutes and be cooled to 60 ℃ with 3 ℃/minute subsequently.By aftertreatment, with fabric with about 5 minutes of cold complete deionized water rinse, and then oxidation.For this reason, handle down through hyperchromatic fabric 15 minutes 4.5,70 ℃ of pH with 10: 1 bath raio with the acetic acid of 1% hydrogen peroxide 35% and 2%.Perhaps, also can carry out solid in two hours and vulcanize right fuel oxidation by being blown into air at 60 ℃.
The fabric after the rinsing dyeing 3 to 5 minutes in the complete deionized water of heat subsequently, rinsing 5 minutes at the most in cold complete deionized water is then extracted and dry.
Electrochemistry dyeing
The color pond of 25ml capacity is separated and is had in use by cationic exchange membrane, total surface area is 2m
23 layers of cylindric stainless steel cathode, scribble the titanium electrode of stainless steel mixed oxide and 0.1M NaOH as anolyte, the C.I.Sulfur Black 1 that comprises 540g is that the catholyte of the NaCl of 50% aqueous sodium hydroxide solution of 33% wet mashed prod, 52ml wetting agent, 210ml and 1.56kg carries out electrolysis, cell voltage was about 8 volts when wherein the starting stage was at the pond of 25A electric current, at 25A, and current density is 125mA/cm
2Reduce.During the course, make dye bath cycle through the material that will be colored with about 351/kg, and as the pumping of sewage discharging current by the cathodic area so that dye bath by with catholyte exchange and regeneration constantly, being colored material is that quality is the mtric count 69 cotton yarn packages of 2700g.
Dyeing procedure comprises a plurality of stages:
1. reduce and the heating phase: in this stage, dye bath is elevated to the dyeing temperature that needs, applies the current density that reducing dyes needs simultaneously.
2. dye and cooling stages: carry out actual dyeing courses at 80 ℃.
3. finish: hydrogen peroxide oxidation, rinsing and dry.
The painted L value that so obtains is 27.11, and a value is+0.66, and the b value is-1.95.
Claims (17)
1. colourless sulfur dye composition, it can be at 50mA/cm
2To 500mA/cm
2Current density and 0.1m/s obtain under the flow velocity of 0.4m/s to 2m/s, preferred 0.1m/s.
2. the colourless sulfur dye composition of claim 1, it can be at 50mA/cm
2To 150mA/cm
2Current density and 0.1m/s under the flow velocity of 0.4m/s, obtain.
3. the mixture of the different colourless sulfur dye composition of claim 1.
4. prepare the method for the colourless sulfur dye composition of claim 1, it comprises from the concentration of 20g/l and 0.5mA/cm
2Initial current density begin, and increase continuously concentration to 600g/l with increase continuously current density to 500mA/cm
2
5. the method for the colourless sulfur dye composition of preparation of claim 4, it further comprises the general formula R-S-SO that adds catalytic amount
3N
aBunte salt, wherein R represents organic repeated structural unit, as phenthiazone, Buprofezin, thianthrene or phenol _ piperazine ketone minor structure; Or by adding the chemical reducing agent of catalytic amount, for example V-Brite B or organic-sulfinic acid and/or organic sugar.
6. the method for claim 4 and 5 the colourless sulfur dye composition of preparation is wherein used large flat electrode or three-diemsnional electrode in the isolated form electrolyzer.
7. the method for the colourless sulfur dye composition of preparation of claim 4, the basic solution that wherein uses an alkali metal salt is as conducting electrolyte.
8. the method for the colourless sulfur dye composition of preparation of claim 4, wherein electrolysis is carried out under 20 ℃ to 135 ℃ temperature.
9. the method for the colourless sulfur dye composition of preparation of claim 4, wherein electrolysis is carried out under 20 ℃ to 95 ℃ temperature.
10. the quinonimine sulfur dye composition of claim 1, when using C.I.Sulfur Black1 as dye material, the concentration of reducing equivalent is that 150Ah/kg is to 534Ah/kg with respect to the drying solid thioxine dyes of 1kg.
11. the method for quinonimine thioxine dyes after the reduction of the present invention of preparation solid form, by make pH be reduced to≤9 and/or the colourless quinonimine thioxine dyes solution drying behind the electrochemical reduction is carried out.
12. the quinonimine sulfur dye composition of claim 1, when using C.I.Vat Blue 43 as dye material, the concentration of reducing equivalent is that 75Ah/kg is to 225Ah/kg with respect to the drying solid dyestuff of 1kg.
13. comprise the dye formulations of the colourless sulfur dye composition of claim 1.
14. the solid dye preparation comprises with respect to whole product, the colourless sulfur dye composition of water content≤5 weight %, preferred≤2 weight %.
15. to cellulose materials dyeing and method for printing, it comprises the colourless sulfur dye composition that uses claim 1.
16. to the painted method of cellulose materials, it comprises and carries out electrochemical reduction with the direct colourless sulfur dye composition of preparation claim 1 in dye bath.
17. the colourless sulfur dye composition of claim 1 is to the application in cellulose materials dyeing and the stamp.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004040601.4 | 2004-08-21 | ||
| DE102004040601A DE102004040601A1 (en) | 2004-08-21 | 2004-08-21 | Novel liquid quinoneimine sulfur dye compositions and processes for their preparation and their use for dyeing cellulosic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1916082A true CN1916082A (en) | 2007-02-21 |
| CN1916082B CN1916082B (en) | 2011-01-26 |
Family
ID=35115890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100927530A Expired - Fee Related CN1916082B (en) | 2004-08-21 | 2005-08-19 | Novel quinonimine sulfur dye compositions, methods for producing them and their use for dyeing cellulose-containing material |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20060288500A1 (en) |
| EP (1) | EP1784457A1 (en) |
| JP (1) | JP2006057094A (en) |
| KR (1) | KR20060053173A (en) |
| CN (1) | CN1916082B (en) |
| BR (1) | BRPI0503682A (en) |
| DE (1) | DE102004040601A1 (en) |
| HK (1) | HK1097285A1 (en) |
| MX (1) | MXPA05008885A (en) |
| TW (1) | TWI417346B (en) |
| WO (1) | WO2006021502A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602287A (en) * | 2016-01-22 | 2016-05-25 | 天津工业大学 | Preparation method of novel composite indigo blue dye of premixed reducing agent |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1906083A1 (en) * | 1969-02-07 | 1970-08-13 | Cassella Farbwerke Mainkur Ag | Process for the production of reduced sulfur dyes |
| AT398316B (en) * | 1989-06-01 | 1994-11-25 | Verein Zur Foerderung Der Fors | METHOD FOR REDUCING DYE |
| US5611818A (en) * | 1991-05-23 | 1997-03-18 | Sandoz Ltd. | Dry leuco sulphur dyes in particulate form |
| AT408455B (en) * | 1997-09-04 | 2001-12-27 | Basf Ag | METHOD FOR REDUCING SULFUR DYES |
| DE10120821A1 (en) * | 2001-04-27 | 2002-10-31 | Sachtleben Chemie Gmbh | A polyalkene coated porous filler useful as a packing material in high performance chromatography is stable towards solvents and strong acids or bases, and avoids excessive preparation costs due to the high solvent volumes required |
| WO2003054286A1 (en) * | 2001-12-20 | 2003-07-03 | Tex-A-Tec Ag | Method and apparatus for electro-catalytical hydrogenation of vat dyes and sulphide dyes |
| DE10234825A1 (en) * | 2002-07-31 | 2004-02-19 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Process for dyeing with sulfur and sulfur vat dyes |
| AU2003273714A1 (en) * | 2002-11-06 | 2004-06-07 | Tex-A-Tec Ag | Method for the electrochemical reduction of vat and sulphur dyes |
-
2004
- 2004-08-21 DE DE102004040601A patent/DE102004040601A1/en not_active Withdrawn
-
2005
- 2005-08-05 WO PCT/EP2005/053880 patent/WO2006021502A1/en active Application Filing
- 2005-08-05 EP EP05771985A patent/EP1784457A1/en not_active Withdrawn
- 2005-08-11 US US11/201,918 patent/US20060288500A1/en not_active Abandoned
- 2005-08-18 TW TW094128231A patent/TWI417346B/en not_active IP Right Cessation
- 2005-08-19 KR KR1020050076242A patent/KR20060053173A/en not_active Application Discontinuation
- 2005-08-19 MX MXPA05008885A patent/MXPA05008885A/en unknown
- 2005-08-19 BR BRPI0503682-8A patent/BRPI0503682A/en not_active IP Right Cessation
- 2005-08-19 CN CN2005100927530A patent/CN1916082B/en not_active Expired - Fee Related
- 2005-08-19 JP JP2005239055A patent/JP2006057094A/en not_active Withdrawn
-
2007
- 2007-04-27 HK HK07104524.0A patent/HK1097285A1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602287A (en) * | 2016-01-22 | 2016-05-25 | 天津工业大学 | Preparation method of novel composite indigo blue dye of premixed reducing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0503682A (en) | 2006-04-04 |
| HK1097285A1 (en) | 2007-06-22 |
| DE102004040601A1 (en) | 2006-03-02 |
| CN1916082B (en) | 2011-01-26 |
| TWI417346B (en) | 2013-12-01 |
| MXPA05008885A (en) | 2006-02-22 |
| EP1784457A1 (en) | 2007-05-16 |
| US20060288500A1 (en) | 2006-12-28 |
| TW200619325A (en) | 2006-06-16 |
| JP2006057094A (en) | 2006-03-02 |
| WO2006021502A1 (en) | 2006-03-02 |
| KR20060053173A (en) | 2006-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1296438C (en) | Black and active dye | |
| CN104030269B (en) | The preparation method of red carbon quantum dot and application | |
| CN106745246B (en) | A kind of method for preparing vanadic sulfate | |
| CN1118520C (en) | Triphendioxazine dyestuffs for dyeing organic substrates | |
| CN1916081A (en) | Technique for producing sumitone fast violet RL | |
| CN1912014A (en) | Dark black active dyestuff having high colour fixing rate | |
| CN1408037A (en) | Electrochemical reduction for reducible dyes | |
| CN103265502B (en) | Preparation method of 2,2'-(4,4'-distylyl) dibenzoxazole by adopting new sulphur method | |
| Kulandainathan et al. | Review of the process development aspects of electrochemical dyeing: its impact and commercial applications. | |
| CN85105802A (en) | The method of the less salt aqueous compositions of preparation fibre-reactive dye | |
| TWI689648B (en) | Dyeing auxiliary, its manufacturing method and applied dyeing process | |
| CN1204203C (en) | Asymmetricazo-based metal complex dye, preparation thereof and acidic black dye composition containing the same | |
| CN1320202C (en) | Electrochemical reduction of dyes | |
| CN102504589B (en) | A kind of turquoise blue dyestuff and its preparation method and application | |
| CN1916082A (en) | Novel quinonimine sulfur dye compositions, methods for producing them and their use for dyeing cellulose-containing material | |
| CN108085711B (en) | A kind of preparation method of the carbon quantum dot to glow | |
| CN104624616B (en) | A kind of indigo production mixes its Future about Alkaline Residue Treatment Unit and processing method | |
| CN1247704C (en) | Dyeing or printing of maunfactured natural polymer and synthetic hydrophobic fibre materials | |
| CN102504588A (en) | Turquoise blue active dye, as well as preparation method and application thereof | |
| CN108191676A (en) | The preparation method of para-aminophenol | |
| CN100351459C (en) | Method for dyeing with sulphur and sulphur vat dyes | |
| CN1130660A (en) | Blue series reactivity dye composition and dye composition blend with same | |
| CN110306360A (en) | A kind of digit printing high stable reactive dye ink and preparation method thereof | |
| CN113549938B (en) | Method for recycling indigo in waste denim laser waste ash | |
| CN116621885B (en) | Recycling treatment method of 2-amino-4-acetamido anisole production wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1097285 Country of ref document: HK |
|
| ASS | Succession or assignment of patent right |
Owner name: DYSTAR COLOURS GERMANY GMBH Free format text: FORMER OWNER: DYSTAR TEXTILFARBEN GMBH + CO. DEUTXCHLAND KG Effective date: 20100916 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20100916 Address after: Frankfurt, Germany Applicant after: Dystar Textilfarben GmbH. & Co. Address before: Frankfurt, Germany Applicant before: Dystar Textilfarben GmbH & Co. Deutxchland KG |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1097285 Country of ref document: HK |
|
| ASS | Succession or assignment of patent right |
Owner name: DYSTAR COLOURS DISTRIBUTION GMBH Free format text: FORMER OWNER: DYSTAR DYES GERMANY CO., LTD. Effective date: 20121019 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20121019 Address after: Frankfurt, Germany Patentee after: DyStar Textilfarben GmbH & Co. Deutschland KG Address before: Frankfurt, Germany Patentee before: Dystar Textilfarben GmbH. & Co. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110126 Termination date: 20140819 |
|
| EXPY | Termination of patent right or utility model |