EP1266069B1 - Mediatorsysteme auf basis gemischter metallkomplexe zur reduktion von farbstoffen - Google Patents
Mediatorsysteme auf basis gemischter metallkomplexe zur reduktion von farbstoffen Download PDFInfo
- Publication number
- EP1266069B1 EP1266069B1 EP01909807A EP01909807A EP1266069B1 EP 1266069 B1 EP1266069 B1 EP 1266069B1 EP 01909807 A EP01909807 A EP 01909807A EP 01909807 A EP01909807 A EP 01909807A EP 1266069 B1 EP1266069 B1 EP 1266069B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mediator
- metal ion
- dyes
- metal
- ions
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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
- 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
- D06P1/22—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 vat dyestuffs including indigo
- D06P1/221—Reducing systems; Reducing catalysts
-
- 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
- D06P1/22—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 vat dyestuffs including indigo
- D06P1/228—Indigo
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65118—Compounds containing hydroxyl groups
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
- D06P1/67358—Halides or oxyhalides
-
- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2016—Application of electric energy
-
- 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
- Y10S8/918—Cellulose textile
Definitions
- the present invention relates to mediator systems obtainable by mixing a salt of an electrochemically active, complex-forming metal (M1), which can form a plurality of valence states, with a hydroxyl group-containing, but no amino complexing agent, which may also be present as a salt, and a salt of an electrochemically inactive also complex-forming metal (M2) in an alkaline aqueous medium, wherein the molar ratio of metal ion M2 to metal ion M1 is 0.9: 1 to 1.1: 1.
- M1 electrochemically active, complex-forming metal
- M2 complex-forming metal
- Vat dyes and sulfur dyes are important classes of textile dyes.
- Vat dyes are of great importance for the dyeing of cellulose fibers, in particular because of the high fastnesses of the dyeings.
- the insoluble oxidized dye When using these dyes, the insoluble oxidized dye must be converted to its alkali-soluble leuco form by a reduction step. This reduced form shows high affinity for the cellulose fiber, absorbs it and is converted to its insoluble form by an oxidation step on the fiber.
- the class of sulfur dyes is of particular importance for the production of lower cost dyes with average fastness requirements.
- it is also necessary to carry out a reduction and oxidation step in order to fix the dye on the goods can.
- the literature describes various reducing agents which are also used industrially, for example sodium dithionite, organic sulfinic acids, organic hydroxy compounds such as glucose or hydroxyacetone. Sulfur dyes and polysulfides are also used in some countries to reduce sulfur dyes.
- a common feature of these reducing agents is the lack of a suitable way to regenerate their reducing action, so that these chemicals are released into the wastewater after use with the dyebath. In addition to the costs of the fresh chemicals to be used also creates additional effort in the treatment of wastewater.
- WO 94/23114 with bicin (N, N-bis (2-hydroxyethyl) glycine) ( WO-A-95/07374 ), with triisopropanolamine ( WO-A-96/32445 ) and with aliphatic hydroxy compounds which may contain a plurality of hydroxyl groups and may additionally be functionalized by aldehyde, keto or carboxyl groups, such as di- and polyalcohols, di- and Polyhydroxyaldehyden, di- and polyhydroxyketones, di- and polysaccharides, di- and Polyhydroxymono and dicarboxylic acids and hydroxytricarboxylic acids, wherein the compounds derived from sugars, in particular the acids and their salts, for example gluconic and heptagluconic acid, and citric acid are emphasized as being preferred ( DE-A-42 06 929 .
- the known mediator systems have certain weaknesses. Although the iron complexes based on triethanolamine or bicin show a sufficiently negative redox potential for the dye reduction, they are not sufficiently stable in the weaker basic range at pH ⁇ 11.5, which severely restricts their electrochemical regenerability in indigo dyebaths during denim production. Although the mediator systems based on gluconate or heptagluconate have very good complex stability in the pH range of 10 to 12, in the known systems a relatively high proportion of iron (II) must be present in order to achieve a redox potential of ⁇ -700 mV ( Ag / AgCl, 3 m KCl reference electrode), as required, for example, to maintain the required bath stability when dyeing with indigo.
- II iron
- the required high proportion of iron (II) complex is disadvantageous, in particular when dyeing with indigo in denim production, since the textile material is dyed in layers by repeated immersion in the dyebath and subsequent air oxidation of the dyestuff, thus completely completing the mediator contained in the dyebath on each aisle is oxidized and must be reduced again for the next Därbegang, which has a high power consumption, which in turn makes for compensation high mediator concentrations or correspondingly large electrolysis cells required.
- the invention therefore an object of the invention to remedy the disadvantages mentioned and to enable the reduction of dyes in an advantageous, economical manner.
- stable mediator systems with good reducing power should be provided. Accordingly, the mediator systems defined above were found.
- the mediator systems according to the invention are obtainable by mixing the individual components, which can be used in the form of their water-soluble salts, in alkaline aqueous medium, which generally has a pH of about 10 to 14.
- the metal ions M1 and M2 are at least partially complexed, preferably forming an approximately equimolar complex.
- the amount of complexing agent is not critical and has at a given ratio of reduced to oxidized form of the metal ion M1 only minor importance. Usually, at least as much complexing agent is used as would theoretically be required for the complete complexation of M1, ie at least 0.5 mol, preferably 1 mol, per mol of M1. An upper limit for this molar ratio does not exist in principle, but for cost reasons, one will usually use not more than 5 mol, in particular 3 mol, especially 1.5 mol, complexing agent per mol of M1.
- the metal ion M1 can be used in both lower and higher valued form.
- iron (II) - and iron (III) salts can be used in the particularly preferred metal iron, which are first reduced electrochemically without problems to iron (II).
- Particularly preferred complexing agents are the monocarboxylic acids derived from sugars, in particular gluconic acid and heptagluconic acid, and their salts, esters and lactones.
- mixtures of the complexing agents can be used.
- a particularly suitable example of this is a mixture of gluconic acid and heptagluconic acid, preferably in a molar ratio of 0.1: 1 to 10: 1, which gives particularly stable iron complexes even at relatively high temperatures.
- Metal ions M2 which are preferably used are metal ions which likewise form stable complexes with the complexing agent according to the invention. Particularly preferred are divalent metal ions, with calcium ions being most preferred.
- mediator systems according to the invention contain, as metal ion M1, iron (II / III) ions, as metal ion M2 calcium ions and as complexing agents gluconic acid and / or heptagluconic acid.
- mediator systems according to the invention are that they not only in the customary for the reduction of dye pH range (about 12.5 to 13.5), but also at low concentration of low-valent metal ion M1 and thus a low concentration of active complex Redox potential ⁇ -700 mV, but also at lower pH, ie form at about 11 to 12, a stable complex system, so are all in all excellent for electrochemical dyeing, especially with indigo as mediators.
- the mediator systems according to the invention are outstandingly suitable for the electrochemical reduction of dyes.
- vat dyes examples include indigo and its bromo derivatives, 5,5'-dibromoindigo and 5,5 ', 7,7'-tetrabromoindigo, and thioindigo, acylaminoanthraquinones, anthraquinonazoles, anthrimides, anthrimidecarbazoles, phthaloylacridones, benzanthrones, and indanthrones, and pyrenchinones, anthanthrones, Pyranthrones, Acedianthrone and perylene derivatives.
- particularly important sulfur dyes are CI Sulfur Black 1 and CI Leuco Sulfur Black 1 and sulfur vat dyes such as CI Vat Blue 43.
- the maximum amount used is usually approximately the amount of mediator required stoichiometrically for the dye reduction.
- 2 mol of a mediator system according to the invention are generally calculated, based on the redox-active, an electron-supplying metal ion.
- this mediator amount can be lowered by the electrochemical regeneration of the mediator (when dyeing with vat dyes, based on a liter of dyebath, usually up to about 0.1 to 1 mol reduced mediator per mole of dye). The greater the deficit in the mediator system, the higher the demands on the electrolysis cell.
- the reduction process according to the invention can advantageously be part of the likewise inventive process for dyeing cellulose-containing textile material with vat and sulfur dyes.
- the dye is added to the dyebath in prereduced form, e.g. an alkaline solution catalytically reduced indigo, and reduces the reoxidized during dyeing by air contact portion of the dye electrochemically using the mediator according to the invention.
- the dyeing itself can be carried out as described in the literature mentioned above. In this case, by all known continuous and discontinuous dyeing methods, e.g. after the exhaust process and the padder process.
- the further process conditions such as type of textile auxiliaries, amounts used, dyeing conditions, type of electrolysis cell, completion of the dyeings, can be selected as usual and described in the literature mentioned above.
- the electrolysis cell was a multi-cathode cell (10 electrodes, 400 cm 2 viewing area, total area 1.9 m 2 ).
- the anolyte used was 5% strength by weight sulfuric acid.
- the separation of catholyte (dyebath) and anolyte was carried out by a cation exchange membrane.
- the cathode used was a stainless steel mesh and the anode used was a platinum mixed oxide coated titanium electrode.
- the cotton yarn was first pre-wetted in a cold wetting agent liquor (3 g / l of a commercial wetting agent) and, after squeezing to 75% liquor pick-up, immersed in the dyebath (11.25 l, room temperature) described below. After a dipping time of about 25 seconds and squeezing to 75% liquor pick-up, the yarn was oxidized in air at room temperature for 120 seconds. This process (“train”), i. Diving into the dyebath, squeezing and air oxidation, was repeated several times. Thereafter, the dyed yarn was rinsed with deionized water and dried.
- a cold wetting agent liquor 3 g / l of a commercial wetting agent
- the dyebath adjusted to pH 11.3 had the following composition:
- the dyebath was reduced before dyeing. After 5 minutes of electrolysis at 5 A, a potential of -700 mV was reached, the cell voltage was 6.6 V. Subsequently, a 20 wt .-%, alkaline aqueous Leukoindigoates (BASF) was added to the reduced dyebath, which then for dyeing has been used.
- BASF alkaline aqueous Leukoindigoates
- Dyes of excellent quality were obtained, which corresponded in color depth and coloration standard dyeings with hydrosulfite as a reducing agent.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10010060 | 2000-03-02 | ||
DE10010060A DE10010060A1 (de) | 2000-03-02 | 2000-03-02 | Mediatorsysteme auf Basis gemischter Metallkomplexe zur Reduktion von Farbstoffen |
PCT/EP2001/002307 WO2001064999A1 (de) | 2000-03-02 | 2001-03-01 | Mediatorsysteme auf basis gemischter metallkomplexe zur reduktion von farbstoffen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1266069A1 EP1266069A1 (de) | 2002-12-18 |
EP1266069B1 true EP1266069B1 (de) | 2009-09-02 |
Family
ID=7633164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01909807A Expired - Lifetime EP1266069B1 (de) | 2000-03-02 | 2001-03-01 | Mediatorsysteme auf basis gemischter metallkomplexe zur reduktion von farbstoffen |
Country Status (13)
Country | Link |
---|---|
US (1) | US6790241B2 (ko) |
EP (1) | EP1266069B1 (ko) |
JP (1) | JP2003525362A (ko) |
KR (1) | KR100683309B1 (ko) |
CN (1) | CN1296553C (ko) |
AT (1) | ATE441756T1 (ko) |
BR (1) | BR0108852A (ko) |
DE (2) | DE10010060A1 (ko) |
ES (1) | ES2330505T3 (ko) |
HK (1) | HK1053156B (ko) |
MX (1) | MXPA02008540A (ko) |
PT (1) | PT1266069E (ko) |
WO (1) | WO2001064999A1 (ko) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004023161A1 (de) * | 2004-05-07 | 2005-11-24 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Elektrolysezelle mit Mehrlagen-Streckmetall-Kathoden |
DE102008058890A1 (de) | 2008-11-26 | 2010-05-27 | Daimler Ag | Gleichlauf-Verschiebegelenk |
CN102383317A (zh) * | 2011-05-31 | 2012-03-21 | 东华大学 | 一种基于石墨电极的电化学还原染色电解液及其应用 |
CN111020661B (zh) * | 2019-12-20 | 2021-06-08 | 河北科技大学 | 一种用于间接电化学染色的电解体系及电化学染色工艺 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT398316B (de) * | 1989-06-01 | 1994-11-25 | Verein Zur Foerderung Der Fors | Verfahren zur reduktion von farbstoffen |
WO1992009740A1 (de) | 1990-12-03 | 1992-06-11 | Verein Zur Förderung Der Forschung Und Entwicklung In Der Textilwirtschaft | Verfahren zur reduktion von textilfarbstoffen |
DE4206929A1 (de) | 1992-03-05 | 1993-09-09 | Basf Ag | Verfahren zum faerben oder bedrucken von cellulosehaltigem textilmaterial mit kuepenfarbstoffen |
DE4230870A1 (de) * | 1992-09-16 | 1994-03-17 | Basf Ag | Verfahren zum Färben und Bedrucken von textilen Materialien aus Cellulosefasern |
TW251325B (ko) * | 1993-03-30 | 1995-07-11 | Basf Ag | |
DE4320867A1 (de) * | 1993-06-24 | 1995-01-05 | Basf Ag | Verfahren zum Färben von cellulosehaltigen Textilmaterialien mit Küpenfarbstoffen oder Schwefelfarbstoffen |
DE4320866A1 (de) | 1993-06-24 | 1995-01-05 | Basf Ag | Verfahren zum Färben oder Bedrucken von cellulosehaltigen Textilmaterialien mit Küpenfarbstoffen oder Schwefelfarbstoffen |
AT402946B (de) | 1993-09-08 | 1997-09-25 | Verein Zur Foerderung Der Fors | Elektrolysezelle |
DE19513839A1 (de) | 1995-04-12 | 1996-10-17 | Basf Ag | Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen |
DE19919746A1 (de) * | 1999-04-29 | 2000-11-02 | Basf Ag | Verfahren zur Herstellung von wäßrig-alkalischen Lösungen reduzierter indigoider Farbstoffe |
-
2000
- 2000-03-02 DE DE10010060A patent/DE10010060A1/de not_active Withdrawn
-
2001
- 2001-03-01 ES ES01909807T patent/ES2330505T3/es not_active Expired - Lifetime
- 2001-03-01 MX MXPA02008540A patent/MXPA02008540A/es active IP Right Grant
- 2001-03-01 AT AT01909807T patent/ATE441756T1/de not_active IP Right Cessation
- 2001-03-01 KR KR1020027011443A patent/KR100683309B1/ko not_active IP Right Cessation
- 2001-03-01 WO PCT/EP2001/002307 patent/WO2001064999A1/de active Application Filing
- 2001-03-01 DE DE50115088T patent/DE50115088D1/de not_active Expired - Lifetime
- 2001-03-01 US US10/220,071 patent/US6790241B2/en not_active Expired - Fee Related
- 2001-03-01 JP JP2001563680A patent/JP2003525362A/ja active Pending
- 2001-03-01 EP EP01909807A patent/EP1266069B1/de not_active Expired - Lifetime
- 2001-03-01 CN CNB018058574A patent/CN1296553C/zh not_active Expired - Fee Related
- 2001-03-01 BR BR0108852-1A patent/BR0108852A/pt not_active Application Discontinuation
- 2001-03-01 PT PT01909807T patent/PT1266069E/pt unknown
-
2003
- 2003-07-24 HK HK03105339.6A patent/HK1053156B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ATE441756T1 (de) | 2009-09-15 |
BR0108852A (pt) | 2003-05-06 |
US6790241B2 (en) | 2004-09-14 |
PT1266069E (pt) | 2009-10-16 |
KR20020087064A (ko) | 2002-11-21 |
CN1406300A (zh) | 2003-03-26 |
EP1266069A1 (de) | 2002-12-18 |
CN1296553C (zh) | 2007-01-24 |
US20030088926A1 (en) | 2003-05-15 |
MXPA02008540A (es) | 2002-12-13 |
HK1053156B (zh) | 2007-06-01 |
DE10010060A1 (de) | 2001-09-06 |
WO2001064999A1 (de) | 2001-09-07 |
DE50115088D1 (de) | 2009-10-15 |
KR100683309B1 (ko) | 2007-02-15 |
ES2330505T3 (es) | 2009-12-11 |
HK1053156A1 (en) | 2003-10-10 |
JP2003525362A (ja) | 2003-08-26 |
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