EP2478060A2 - Procede de teinture utilisant des colorants naturels - Google Patents

Procede de teinture utilisant des colorants naturels

Info

Publication number
EP2478060A2
EP2478060A2 EP10739310A EP10739310A EP2478060A2 EP 2478060 A2 EP2478060 A2 EP 2478060A2 EP 10739310 A EP10739310 A EP 10739310A EP 10739310 A EP10739310 A EP 10739310A EP 2478060 A2 EP2478060 A2 EP 2478060A2
Authority
EP
European Patent Office
Prior art keywords
dye
precipitate
aqueous medium
dyeing
acid
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.)
Withdrawn
Application number
EP10739310A
Other languages
German (de)
English (en)
Inventor
Thomas Bechtold
Christa Fitz-Binder
Amalid Mahmud-Ali
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitaet Innsbruck
Original Assignee
Universitaet Innsbruck
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universitaet Innsbruck filed Critical Universitaet Innsbruck
Publication of EP2478060A2 publication Critical patent/EP2478060A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
    • 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
    • C09B63/00—Lakes
    • C09B63/005—Metal lakes of 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
    • D06P1/34—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 natural dyestuffs

Definitions

  • the invention relates to a method for producing a solution containing a dye of biological material. Furthermore, the invention relates to a method for dyeing a substrate, preferably textile, by means of a dye of biological material.
  • dyes colored with pigments and with pigments include the historical dyes.
  • Dyes are in dissolved form for the dyeing process and show affinity / substantivity to the substrate, the material to be dyed.
  • Pigments e.g. Ingredients in artist paints and varnishes are in insoluble form and have no affinity for the material to be dyed. It is therefore an appropriate matrix to provide a binder system whereby the pigment is bound to the carrier.
  • pigment dyeing where binder systems must be used in a targeted manner, when dyeing textiles and leather dyes are applied from their, usually in water, dissolved form and fixed by various processes on the substrate.
  • Natural dyes are substances that are obtained from biological material, such as from vegetable and to a small extent from animal sources of raw materials, by extraction and serve to color a substrate.
  • the extraction can be carried out in aqueous solution or by addition of chemicals.
  • the literature recommends the addition of alkalis such as soda or caustic soda, of acids or of solvents.
  • alkalis such as soda or caustic soda, of acids or of solvents.
  • the aim of these concepts is to produce as concentrated an extract as possible of extracted plant / animal origin.
  • Extracting the dyes with a solvent or with the addition of chemicals dramatically degrades the resource balance of the dye recovery and removes an ecologically unmanageable amount of chemicals from the process with the extracted material. It comes therefore for a lasting extraction of the Natural dyes only water as extractant in question. For the production of concentrated products a substantial removal of the water used in the extraction is necessary. However, water has a very high specific heat of vaporization.
  • the dye concentrates provided according to the prior art therefore do not meet the requirements for ecological and resource-conserving products and are therefore more likely to be regarded as marketing products.
  • a critical examination of the aspects of sustainability, energy consumption and resource consumption shows that the concentration step always leads to a deterioration in the overall balance.
  • a resource-saving extraction by aqueous extraction and the immediate use of the extracts for dyeing purposes takes place locally in the textile dyeing.
  • the relatively dilute aqueous extracts are used directly in the dyeing plants.
  • a concentration can be avoided, but the achievable color depths are limited and the process is limited to techniques with "long liquor", ie with a high ratio of volume dyebath to commodity eg 20: 1.
  • color lakes and pigments the extracted dye is deliberately converted by the addition of precipitants such as metal salts in an insoluble form.
  • precipitants such as metal salts in an insoluble form.
  • the precipitation of natural dyes is known as color lakes. These are insoluble pigments that are suitable for artistic purposes, but not for dyeing textile products. As already described, pigments as insoluble color bodies no longer have any affinity for the substrate and are therefore unsuitable as dyes.
  • the precipitation of tannin with aluminum salts to form insoluble aluminum complexes is known and is used for example as an anti-fouling component in boat paints.
  • the pickling process by the dyeing process is carried out separately as a pre- or Nachbeize, since here at least the pickling baths can be reused. If the meta-pickling process is used, the stain is added directly to the dyebath, making re-use of the dyebath impossible due to the presence of undissolved pigments.
  • a crucial difficulty in the use of natural dyes therefore lies in the problem of either having to use dilute aqueous solutions or to spend a large amount of resources for concentration. Both solutions limit or prevent the more extensive use of natural color fabrics as sustainable dye systems.
  • insoluble color lakes does not provide a solution to the issue, since the insoluble pigments are not suitable for dyeing and therefore only for use as painter pigments etc. can be used.
  • GB 1857 01390 A (Cowper) describes the preparation of solutions and extracts of madder and other plant materials. By adding metal ions, a precipitation of the dissolved dye takes place.
  • GB 1 119 359 describes the extraction of dyes from grape skins in hydrochloric acid solution and the subsequent precipitation with CaCl 2 . The precipitate can then be redissolved in HCl.
  • DE 172 662 mentions a process in which a lake of color is prepared by adding metal ions from a woodlog or yellow wood extract. The paint can be resumed by organic acids. A similar process is disclosed in GB 1877 00674.
  • Object of the present invention is to provide methods of the type mentioned, in which the disadvantages of the prior art are reduced.
  • d Transferring the dye from the dye precipitate in an aqueous solution by adding a releasing agent, wherein the release agent is a complexing agent selected from the group of polycarboxylates, polycarboxylic acids, aminopolycarboxylic acids, such as NTA or EDTA, oxalate, gluconate, citrate, phosphate, polyphosphate or combinations thereof.
  • a releasing agent selected from the group of polycarboxylates, polycarboxylic acids, aminopolycarboxylic acids, such as NTA or EDTA, oxalate, gluconate, citrate, phosphate, polyphosphate or combinations thereof.
  • the release agent is a complexing agent selected from the group of polycarboxylates, polycarboxylic acids, aminopolycarboxylic acids, such as NTA or EDTA, oxalate, gluconate, citrate, phosphate, polyphosphate or combinations thereof.
  • the present invention thus overcomes the problem of the low concentration of the dye in the extract by providing a method for resource-saving production of a dye concentrate by precipitation and enrichment, wherein the precipitates are carried out so that the dye in the dyeing process according to the invention is soluble again and thus on the to be dyed Can raise well.
  • the step of the present invention is primarily to provide a suitable dye recovery process, a suitable dye formulation, and a suitable dyeing process which can usefully utilize these precipitates.
  • an aqueous dye extract of the biological material is first prepared (step a).
  • the step a ie the transfer of the dye from biological material into an aqueous medium is carried out by pure water or at most with the auxiliaries mentioned below.
  • this step should be done without organic solvent.
  • suitable precipitant takes place the formation of an insoluble precipitate (step b).
  • the precipitation should proceed in such a way that at least part of the precipitant forms part of the precipitate, ie it is incorporated in the precipitate. This can be done according to the invention in two ways. On the one hand, the precipitant can chemically react with the dye and form the precipitate.
  • the precipitating agent may comprise metal ions which form a complex or salt with the dye.
  • the precipitant in this case is selected such that the complex or salt has a lower solubility product than the dye with the other materials in the solution. Part of the precipitant (eg the metal ions) is thus chemically bound in the precipitate.
  • the precipitant itself can form a precipitate and absorb the dye without chemical bonding. In this case, the dye is adsorbed on the precipitate.
  • the precipitate is concentrated by separating it from the aqueous medium (step c).
  • step a In processes for preparing a solution containing a dye, a solution with a higher concentration of dye is actually prepared than can be obtained by simple extraction (step a).
  • An essential step is the final transfer of the dye from the dye precipitate in an aqueous solution by adding a release agent.
  • the desired concentration of dye in the aqueous solution can be adjusted.
  • the dyeing process is modified in the procedure according to the invention so that the dye concentrate or the pigment preparation first releases the dye again, then the dyeing process is carried out.
  • the release of the dye can also be carried out in the presence of the substrate (step d in the process for dyeing a substrate).
  • the dye concentrate or pigment concentrate is precipitated as a dye preparation by precipitation of the dye from the aqueous extract of the plant material by using precipitants, preferably metal salt ions, particularly preferably salts of the cations iron, calcium, aluminum, magnesium, titanium.
  • adjuvants such as caustic soda, soda, ammonia, inorganic and organic acids for pH adjustment, as well as other chemicals that promote precipitation, such as phosphates, silicates or polyelectrolytes, can be added. These adjuvants may serve to improve the extraction yield and / or to favor the precipitation of the extracted dye.
  • the precipitation pH is adjusted.
  • the addition of the metal salt takes place in dissolved form.
  • Typical examples of precipitants are FeSO 4 , KA 1 (SO 4 ) 2 or (NH 4 ) 2 Fe (SO 4 ) 2.
  • the amounts of precipitant used in the precipitation depend on the extract strength, usually concentrations below 100 g / l precipitant, preferably to use metal salt, advantageous concentrations below 50 g / l precipitant, preferably metal salt, in a particularly preferred embodiment are between 5 , 0 and 0.1 g / l precipitant, preferably metal salt used.
  • the pH of the solution depends on the solubility behavior of the metal ions used and the need for chemicals to adjust the pH. A working range between pH 2 and pH 12 is advantageous, and the precipitation takes place particularly advantageously at pH values between 4 and 10.
  • the insoluble dye product formed by precipitation is concentrated by sedimentation and filtration and can be provided as an aqueous dispersion or as a dried and ground product for the following dyeing process.
  • Other forms of concentration are possible, e.g. Centrifugation, spray drying etc.
  • Plant dyes which are suitable for the procedure according to the invention originate, for example, from the group of flavonoid dyes, but others may also be used Dyes, for example anthraquinoid dyes, indigoid dyes and dyes from the group of polyphenols can be obtained and used by the process according to the invention.
  • Dyes for example anthraquinoid dyes, indigoid dyes and dyes from the group of polyphenols can be obtained and used by the process according to the invention.
  • the selection of the precipitant is done carefully. It is advantageous to use such precipitating agents that are compatible for the desired dyeing process, do not interfere with the dyeing process during the dissolution of the pigment, or can be so blocked / masked during the dyeing process that it is not hindered.
  • the treatment of the pigment with a suitable chemical which is able to cleave the dye pigment and release the original dye again.
  • a suitable chemical which is able to cleave the dye pigment and release the original dye again.
  • suitable for this purpose are complexing agents from the group of polycarboxylates and polycarboxylic acids, aminophenylcarboxylic acids such as NTA (nitrilotriacetic acid) and EDTA (ethylenediaminetetraacetate), oxalate, gluconate, citrate and phosphates or polyphosphates, which can dissolve a precipitate formed.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetate
  • oxalate gluconate
  • citrate and phosphates or polyphosphates which can dissolve a precipitate formed.
  • admix acids which are particularly preferably selected from the group consisting of acetic acid, hydrochloric acid, citric acid, gluconic
  • the dye pigment which is unsuitable for dyeing is thus dissolved in the dissolution step, for example by treatment with, for example, acid or complexing agents, by mobilizing the precipitation agent causing the precipitation, such as the metal ion, by pH shift or complex formation.
  • the conditions to be used are advantageously selected so that the dye molecule is not adversely affected.
  • the dyestuff solution thus obtained can now be used for dyeing by adding it to the prepared dyebath.
  • the dyeing is carried out according to the usual dyeing process for natural dyes, it can be used as desired pickling and pickling. When using metal stains care must be taken that the chemicals used to dissolve the dye pigment do not bind the added stain as well. However, knowing the procedure according to the invention, this can be easily corrected by using a sufficiently increased amount of pickling that the amount of free metal ion required for pickling dyeing is available.
  • precipitants and / or release agents are added to the substrate during the dyeing step to determine the desired shade. It is thus possible to adjust the color on the substrate at any time.
  • suitable release agents, or precipitants in addition to the different brightness and other shades can be released.
  • the precipitation of the dyes extracted from goldenrod can be accomplished by the addition of iron salts to the olive-dark precipitate, after complexation of the iron upon redissolution of the salt, e.g. by oxalate, then a yellow dyeing on wool can be done using aluminum stains.
  • the dissolution of the pigment form is carried out by acid without complexing agent and the restoration of the complex on the fiber to be dyed by simply raising the pH in the dyebath.
  • the procedure described allows the energy and resource-saving production of a concentrated natural dye product, as it is particularly suitable for the market of ecologically oriented manufacturers and consumers.
  • the formation of precipitate leads to a very high concentration, so that the application of the product is also suitable for processes which require relatively high dye concentrations, eg. continuous dyeing and printing techniques.
  • the method is therefore suitable for all classes of textile fibers, particularly preferred are high-receptivity materials for natural color fabrics such as wool, silk, linen, polyamide.
  • high-receptivity materials for natural color fabrics such as wool, silk, linen, polyamide.
  • the color change is characterized by measuring the color coordinates as CIELab values.
  • a * red - green
  • b * yellow - blue
  • the CIE Lab system is a color space defined by the International Commission on Illumination (Commission Internationale d'Eclairage, CIE 1976).
  • Table 1 shows the color coordinates of the colorations obtained after dissolution of the precipitate in various acids (oxalic acid, gluconic acid, citric acid and hydrochloric acid) on woolen yarn.
  • 50 g of goldenrod are boiled in 1 liter of water for 60 minutes and filtered through a cloth.
  • 100 ml of extract were with 10 ml of a pickling with 50 g / l salt concentration (FeSO 4 , KA1 (SO 4 ) 2 or (NH 4 ) 2 Fe (SO 4 ) 2 ) precipitated and with ammonia solution to pH 5, 7 or 9 set.
  • the solution is heated for a further 35 minutes on the water bath at 80-90 0 C and then allowed to stand overnight at room temperature.
  • the precipitate is filtered through a paper feeder.
  • 1.1 to 1.5 g of a yellow-olive precipitate are obtained (Table 3).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'une solution contenant un colorant, ou sur un procédé de coloration d'un substrat caractérisé par les étapes de : a. transfert du colorant issu de matière biologique dans un milieu aqueux, b. précipitation du colorant à partir du milieu aqueux par addition d'un agent de précipitation approprié, au moins une partie de l'agent de précipitation formant une partie du précipité de colorant, c. séparation du précipité de colorant du milieu aqueux et d. transfert du colorant à partir du précipité de colorant dans une solution aqueuse par addition d'un agent de libération ou de coloration du substrat avec une solution aqueuse dans laquelle le colorant provenant du précipité de colorant est libéré par addition d'un agent de libération dans la solution aqueuse, caractérisé par le fait que l'agent de libération est un agent complexant choisi dans le groupe comprenant les polycarboxylates, des acides polycarboxyliques, des acides aminopolycarboxyliques comme le NTA ou l'EDTA, l'oxalate, le gluconate, le citrate, le phosphate, le polyphosphate ou des combinaisons de ceux-ci.
EP10739310A 2009-07-28 2010-07-16 Procede de teinture utilisant des colorants naturels Withdrawn EP2478060A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT11832009A AT508000B1 (de) 2009-07-28 2009-07-28 Naturfarbstoffe
PCT/EP2010/060339 WO2011012471A2 (fr) 2009-07-28 2010-07-16 Colorant naturel

Publications (1)

Publication Number Publication Date
EP2478060A2 true EP2478060A2 (fr) 2012-07-25

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ID=42937612

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10739310A Withdrawn EP2478060A2 (fr) 2009-07-28 2010-07-16 Procede de teinture utilisant des colorants naturels

Country Status (3)

Country Link
EP (1) EP2478060A2 (fr)
AT (1) AT508000B1 (fr)
WO (1) WO2011012471A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181357A (zh) * 2018-09-12 2019-01-11 乐象永续科技（杭州）有限公司 色淀的制备方法、色淀和应用
CN114561819B (zh) * 2022-03-28 2024-01-30 广东溢达纺织有限公司 一种环保多色面料或者成衣及其炒色加工方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE172662C (fr) *
GB1119359A (en) 1965-10-28 1968-07-10 Upravlenie Vinodelcheskoi Prom Method for the production of eno dyestuff from extracts of grape husks
EP1798262A1 (fr) * 2005-12-15 2007-06-20 Lcw - Les Colorants Wackherr Laques de colorants bleues comprenant des colorants naturels

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011012471A2 *

Also Published As

Publication number Publication date
WO2011012471A3 (fr) 2011-04-14
AT508000B1 (de) 2010-10-15
AT508000A4 (de) 2010-10-15
WO2011012471A2 (fr) 2011-02-03

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