EP3662105A1 - Verfahren zur entfernung von manganoxid-ablagerungen von textilen oberflächen - Google Patents
Verfahren zur entfernung von manganoxid-ablagerungen von textilen oberflächenInfo
- Publication number
- EP3662105A1 EP3662105A1 EP18789120.5A EP18789120A EP3662105A1 EP 3662105 A1 EP3662105 A1 EP 3662105A1 EP 18789120 A EP18789120 A EP 18789120A EP 3662105 A1 EP3662105 A1 EP 3662105A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- ascorbic acid
- treatment
- organic carboxylic
- mixture
- 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.)
- Pending
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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
-
- 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
- D06P1/653—Nitrogen-free carboxylic acids or their salts
- D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
-
- 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
- D06P5/13—Fugitive dyeing or stripping dyes
- D06P5/132—Fugitive dyeing or stripping dyes with oxidants
-
- 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
- D06P5/15—Locally discharging the dyes
- D06P5/153—Locally discharging the dyes with oxidants
-
- 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
Definitions
- the invention relates to a process for the removal of manganese oxide deposits of, for example, indigo and / or sulfur black dyed textiles which have been subjected to a bleaching treatment with, for example, potassium permanganate using mixtures of ascorbic acid and organic carboxylic acids and the use of such mixtures for the removal of manganese oxides.
- wash out and used-look effects means that most of the denim articles dyed with indigo or other dyes are further processed by washing processes, often in combination with chemical treatments, wholly or locally, usually on exposed areas. brightened or bleached.
- Bleaching treatment is often preceded by abrasive scrubbing with enzymes and / or pumice stones.
- the bleaching treatment itself may be done in a second bath containing a bleaching agent to further lighten the color of the entire article and to enhance light-dark contrasts.
- the targeted, local brightening of the articles in correspondingly exposed areas is used as an essential means of, for example, making a pair of jeans really to give aesthetic appearance.
- the denim surface is first locally limited, for example, on the thighs and buttocks, mechanically roughened by grinding. Subsequently, sprayed at these points with a bleaching solution that destroys the dye more or less, depending on the desired intensity of the whitening effect.
- a very commonly used bleaching agent to achieve such lightening effects is potassium permanganate. Especially for the partial bleaching of denim articles by spraying, its use is state of the art.
- permanganate as a dilute, aqueous solution has advantages in practical application: the bleaching action takes place very rapidly within a few minutes, no elevated temperatures are necessary; the bleach itself is storage stable and the bleaching effect achieved is well reproducible.
- a disadvantage is, inter alia, that in the oxidation of the indigo itself, the permanganate ion, which is readily soluble in water, is itself converted predominantly into insoluble manganese oxides, especially manganese dioxide (manganese dioxide).
- manganese dioxide manganese dioxide
- Common reducing agents are sulfur compounds such as sodium hydrogen sulfite, sodium metabisulfite, as described for example in US 4,795,476, or sodium dithionite.
- a disadvantage is a strong odor and a pollution of the wastewater by excess reducing agent due to the high chemical oxygen demand (COD).
- COD chemical oxygen demand
- the neutralization step can not be used for cellulase treatment.
- hydroxylammonium salts such as bis (hydroxylammonium) sulfate are classified as presumably carcinogenic and organ damaging and also have a very high aquatic toxicity.
- vitamin C ascorbic acid
- CN1126245 describes the use of ascorbic acid solutions to leach milled manganese ore.
- WO 2014/111267 proposes the use of a combination of ascorbic acid and hydroxyethanediphosphonic acid (HEDP) to remove metal oxides from textiles or textile surfaces.
- HEDP hydroxyethanediphosphonic acid
- the object of the present invention is now to provide a process for the treatment of textiles, which in particular with indigo and / or sulfur black, optionally in combination with other dyes, dyed and then a bleaching treatment, in particular with permanganates, were subjected to the Bleaching treatment incurred deposits or stains with manganese oxides, especially with manganese dioxide to remove.
- the process is intended to provide comparable results in its cleaning effect as using sulfur-based reducing agents or hydroxylammonium salts, while significantly reducing possible disadvantages and risks for the environment and the user.
- no environmentally hazardous or harmful to human health chemicals should be used and an entry of aquatic toxic substances into the wastewater should be excluded.
- the method should be feasible with economical quantities quickly and effectively.
- the object underlying the invention is achieved by a method for removing manganese oxides from textile fabrics, wherein the textile fabrics are treated with a mixture comprising ascorbic acid and at least one further organic carboxylic acid.
- the inventive combination of ascorbic acid and at least one other organic carboxylic acid the effectiveness of ascorbic acid can be drastically increased or the required amounts can be significantly reduced.
- ascorbic acid means both ascorbic acid (CAS number 50-81-7) and isoascorbic acid (CAS number 89-65-6). Both forms of ascorbic acid each comprise two enantiomers.
- the term ascorbic acid as used in the context of the present invention thus comprises a total of four isomeric forms. These are called L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid and D-isoascorbic acid.
- the four mentioned forms can be used alone or in any mixtures, wherein all four forms or only three or two of the isomeric forms can be contained in a mixture.
- a racemate of L-ascorbic acid and D-ascorbic acid can be used.
- L-isoascorbic acid and D-isoascorbic acid can be used.
- Suitable organic acid further low molecular weight organic carboxylic acids such as acetic acid, glycolic acid or lactic acid. Particularly effective are chelating polybasic acids such as citric acid, which is believed to have an additional synergistic effect due to its complexing effect on metal ions, without the invention being limited thereto by this theory.
- textile materials are used which contain manganese oxides which originate from a previous treatment with permanganates.
- the treatment according to the invention of the textiles contaminated with manganese oxide can take place in a long liquor in a conventional washing unit, for example a drum washing machine, at room temperature or slightly elevated temperature, for example up to 50 ° C.
- the wash liquor is a mixture comprising ascorbic acid and other organic acids in a preferred weight ratio of 1: 9 to 1: 1, in particular in the ratio 1: 5 to 1: 2 added.
- the amount of acid mixture added is preferably between 0.5 g / l and 5.0 g / l, depending on the degree of soiling of manganese oxide.
- the at least one further organic carboxylic acid is selected from the group of mono-, di- or trifunctional low molecular weight carboxylic acids, in particular those having up to 8 C atoms. Also optionally used further carboxylic acids are preferably derived from the groups mentioned here.
- Preferred monofunctional organic carboxylic acids include acetic acid, glycolic acid, lactic acid, formic acid, and propionic acid.
- Preferred difunctional organic carboxylic acids include tartaric, malonic, maleic, fumaric, oxalic, succinic, oxosuccinic, glutaric, adipic and aspartic acids.
- Preferred trifunctional organic carboxylic acids include citric acid and (2R, 3S) iso-citric acid.
- the at least one further organic carboxylic acid is particularly preferably a chelate-forming carboxylic acid. Most preferred is citric acid.
- Thickening agents, dyes, wetting agents, dispersants, complexing agents, enzymes and / or further auxiliaries known per se can be added as further additives to the treatment liquor.
- the mixture used according to the invention comprises an aqueous solution which contains ascorbic acid and at least one further organic carboxylic acid, in particular citric acid.
- the inventive method is preferably carried out at a temperature of 20 to 60 ° C. Particularly preferred is a temperature between 20 and 40 ° C.
- the treatment is carried out in a preferred embodiment of the method according to the invention over a period of 5 to 40 minutes, more preferably over a period of 5 to 20 minutes.
- the pH of the liquor is preferably from 3.0 to 6.0. More preferably, the pH of the manganese oxide removing effect is 3.5 to 5.5, and more preferably 4.0 to 5.0.
- textile fabrics made of cellulose fibers or of cellulose fibers are used in mixture with natural or synthetic fibers which are wholly or partly dyed with different dyes.
- the process according to the invention is preferably carried out with textile materials which are dyed with indigo and / or sulfur black and, if appropriate, in combination with vat, direct, sulfur or disperse dyestuffs.
- the process according to the invention is capable of removing manganese oxide deposits which have arisen both as part of a full bleach with permanganate, for example from a long liquor, and in the case of a local bleach at certain locations of an article, for example in the spray process.
- the object underlying the invention is achieved by the use of a mixture comprising ascorbic acid and at least one further organic carboxylic acid, in particular citric acid, and optionally water for removing manganese oxides from textile materials.
- the determination of the effectiveness of the manganese oxide removal was carried out by two different methods: • Colorimetric measurement of the bleached and neutralized samples and determination of the dimension b * or the color difference Ab to CIELAB with Datacolor International SF 600 plus CT, aperture 30 mm LAV, quadruple measurement, calibration standard light D 65.
- the dimension b * allows the weight of the blue / yellow color component between - 80 (pure blue) and + 80 (pure yellow)
- citric acid (Comparative Example 7) can probably reduce the manganese content due to the complexing properties with respect to metal ions, the optical effect remains strongly behind the combination with ascorbic acid and the color difference Ab still clearly indicates the brownish-yellow discoloration due to manganese oxide residues.
- Example 8 In the case of acetic acid (Comparative Example 8), optically almost no effect of the treatment is evident (Ab negligible in both materials) and only in material 2 was the manganese content reduced somewhat.
- Example 1 In the case of acetic acid (Comparative Example 8), optically almost no effect of the treatment is evident (Ab negligible in both materials) and only in material 2 was the manganese content reduced somewhat.
- Example 1 In the case of acetic acid (Comparative Example 8), optically almost no effect of the treatment is evident (Ab negligible in both materials) and only in material 2 was the manganese content reduced somewhat.
- Example 1 In the case of acetic acid (Comparative Example 8), optically almost no effect of the treatment is evident (Ab negligible in both materials) and only in material 2 was the manganese content reduced somewhat.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Coloring (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102017125010.7A DE102017125010A1 (de) | 2017-10-25 | 2017-10-25 | Verfahren zur Entfernung von Manganoxid-Ablagerungen von textilen Oberflächen |
DE102018101060.5A DE102018101060A1 (de) | 2018-01-18 | 2018-01-18 | Verfahren zur Entfernung von Manganoxid-Ablagerungen von textilen Oberflächen |
PCT/EP2018/078352 WO2019081290A1 (de) | 2017-10-25 | 2018-10-17 | Verfahren zur entfernung von manganoxid-ablagerungen von textilen oberflächen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3662105A1 true EP3662105A1 (de) | 2020-06-10 |
Family
ID=63896185
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18789120.5A Pending EP3662105A1 (de) | 2017-10-25 | 2018-10-17 | Verfahren zur entfernung von manganoxid-ablagerungen von textilen oberflächen |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP3662105A1 (de) |
BR (1) | BR112020004613A2 (de) |
CO (1) | CO2020002330A2 (de) |
MX (1) | MX2020002536A (de) |
WO (1) | WO2019081290A1 (de) |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2040546B1 (de) | 1970-08-14 | 1971-12-02 | Hagen Feldmann | Waessrige Loesung einer aliphatischen Carbonsaeure zur Entfernung von Verockerungen oder Ablagerungen |
JPS596919B2 (ja) | 1981-08-17 | 1984-02-15 | 富士通株式会社 | ロ−ルメッキ法 |
CN86103060A (zh) * | 1986-04-27 | 1987-04-22 | 刘能振 | 由高锰酸盐和还原性物质组成的漂白剂 |
DE3625280A1 (de) | 1986-07-25 | 1988-02-04 | Feldmann Hagen | Reiniger fuer trinkwasseranlagen |
US4795476A (en) | 1988-01-27 | 1989-01-03 | General Chemical Corporation | Method for permanganate bleaching of fabric and garments |
US5066306A (en) | 1989-08-01 | 1991-11-19 | 501 P.B. & S. Chemical Company, Inc. | Process for removing permanganate stains from articles |
US5006124A (en) | 1989-12-15 | 1991-04-09 | Fmc Corporation | Wet processing of denim |
US5205835A (en) | 1991-02-07 | 1993-04-27 | Fmc Corporation | Process to remove manganese dioxide from wet process denim fibers by neutralizing with peracetic acid |
JPH0657627A (ja) | 1992-06-10 | 1994-03-01 | Fmc Corp | 繊維から二酸化マンガンを除去するための過酸化水素及びホスホン酸の使用 |
AT401274B (de) * | 1993-11-23 | 1996-07-25 | Degussa Austria Gmbh | Verfahren zum bleichen von textilartikeln |
US5686014A (en) * | 1994-04-07 | 1997-11-11 | The Procter & Gamble Company | Bleach compositions comprising manganese-containing bleach catalysts |
CN1037784C (zh) | 1994-10-28 | 1998-03-18 | 北京矿冶研究总院 | 一种氧化锰矿石的抗坏血酸还原浸出方法 |
WO2014111267A1 (en) | 2013-01-17 | 2014-07-24 | Archroma Ip Gmbh | System for the removal of iron oxide from surfaces |
-
2018
- 2018-10-17 WO PCT/EP2018/078352 patent/WO2019081290A1/de unknown
- 2018-10-17 BR BR112020004613-2A patent/BR112020004613A2/pt not_active Application Discontinuation
- 2018-10-17 EP EP18789120.5A patent/EP3662105A1/de active Pending
- 2018-10-17 MX MX2020002536A patent/MX2020002536A/es unknown
-
2020
- 2020-03-02 CO CONC2020/0002330A patent/CO2020002330A2/es unknown
Also Published As
Publication number | Publication date |
---|---|
CO2020002330A2 (es) | 2020-06-19 |
WO2019081290A1 (de) | 2019-05-02 |
BR112020004613A2 (pt) | 2020-09-24 |
MX2020002536A (es) | 2020-10-01 |
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