WO2001004410A1 - A method of dyeing natural textile fibres with a dyeing medium comprising supercritical carbon dioxide - Google Patents

A method of dyeing natural textile fibres with a dyeing medium comprising supercritical carbon dioxide Download PDF

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Publication number
WO2001004410A1
WO2001004410A1 PCT/EP2000/006414 EP0006414W WO0104410A1 WO 2001004410 A1 WO2001004410 A1 WO 2001004410A1 EP 0006414 W EP0006414 W EP 0006414W WO 0104410 A1 WO0104410 A1 WO 0104410A1
Authority
WO
WIPO (PCT)
Prior art keywords
dyeing
fibres
dye
carbon dioxide
supercritical carbon
Prior art date
Application number
PCT/EP2000/006414
Other languages
French (fr)
Inventor
Silvio Sicardi
Mario Frigerio
Original Assignee
Ministero Dell'universita' E Della Ricerca Scientifica E Tecnologica
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 Ministero Dell'universita' E Della Ricerca Scientifica E Tecnologica filed Critical Ministero Dell'universita' E Della Ricerca Scientifica E Tecnologica
Priority to AU68224/00A priority Critical patent/AU6822400A/en
Publication of WO2001004410A1 publication Critical patent/WO2001004410A1/en

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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
    • D06P1/94—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 dyes dissolved in solvents which are in the supercritical state
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • 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

Definitions

  • the present invention relates to a method of dyeing textile fibres with the use of a dyeing medium comprising supercritical carbon dioxide and a dye.
  • Supercritical carbon hydroxide has been used with success in methods for dyeing synthetic fibres, for example, polyesters and polyamides, but the results of its use in the dyeing of natural fibres, for example, wool, cotton or silk fibres, have not been so satisfactory.
  • Disperse dyes which are normally used for dyeing synthetic fibres, are in fact apolar and soluble in supercritical carbon dioxide, thus permitting vivid and fast dyeing of chemical fibres; these dyes do not, however, have an affinity to natural fibres which are essentially polar.
  • the object of the present invention is therefore to provide a method of dyeing natural textile fibres with the use of a dyeing medium comprising supercritical carbon dioxide and a dye, which can ensure satisfactory and persistent adhesion of the dye to the fibres .
  • This object is achieved by means of a method of the type indicated at the beginning of the present description and characterized in that the dye is of the water-soluble, polar type, and in that the dyeing medium also comprises a polar co-solvent .
  • polar dyes can be rendered soluble in supercritical carbon dioxide in which they would otherwise be insoluble, and can thus be brought into contact with the natural fibres for which they have a chemical affinity and on which they can effectively perform their dyeing action which is persistent over time and resistant to washing.
  • the co-solvent is preferably selected form the group consisting of methanol, ethanol, water and mixtures thereof.
  • the water-soluble polar dye is preferably of the reactive, direct, cationic, or acid type or the like.
  • concentration of the co-solvent in the dyeing medium is advantageously between 2 and 20% and even more preferably between 5 and 10%. These concentrations, as well as all of those given in the remaining part of the present description, in the absence of any indication to the contrary, should be understood as molar concentrations relative to the moles of C0 2 in the working conditions .
  • the natural textile fibres which can be dyed by the method of the invention are of substantially any nature, for example, fibres and hair of animal origin, vegetable fibres, and mixtures thereof, particularly wool, cotton and silk fibres .
  • the general parameters of the dyeing method of the invention are preferably between 70 and 250 bars with regard to pressure, and between 50 and 120°C with regard to temperature .
  • Dyeing tests were performed in a 1 litre autoclave with a stirrer on samples in the form of small skeins of wool each weighing about 2 g, with a dyeing medium comprising: supercritical C0 , ethanol as a co-solvent at a molar concentration of about 10% relative to the C0 2 , and a quantity of about 1 g, or in any case such as to ensure saturation of the dye bath, of a reactive dye.
  • the dyeing was carried out for about 2 hours at a pressure of about 200 bars and a temperature of about 90°C. Upon completion of this operation, the autoclave was emptied by depressurization in a single step. The dyed samples were then subjected to rapid washing in running water. The dyed samples had good colour intensity, good colour- fastness upon washing, and good light-fastness values.
  • the dyed samples had good colour intensity, reasonable colour-fastness upon washing, and good light-fastness values .
  • Example 2 The tests relating to this example were carried out in similar conditions to those of Example 1 with the difference that a skein of silk was dyed. Moreover, whereas in some tests the same co-solvent was used as in Example 1, in others water at a molar concentration of 2% was used instead.
  • the dye samples had very good colour intensity, good colour- fastness upon washing, and good light-fastness values.

Abstract

The method of dyeing natural textile fibres with the use of a dyeing medium comprising supercritical carbon dioxide and a dye provides for the dye to be of the water-soluble, polar type and for the dyeing medium also to comprise a polar cosolvent. The latter is preferably selected from the group consisting of methanol, ethanol, water and mixtures thereof.

Description

A method of dyeing natural textile fibres with a dyeing medium comprising supercritical carbon dioxide
The present invention relates to a method of dyeing textile fibres with the use of a dyeing medium comprising supercritical carbon dioxide and a dye.
Methods of this type have been the subject of considerable interest in recent years, since they are particularly suitable from an ecological/toxicological point of view and are technologically practicable at costs competitive with those of conventional methods which provide for the use of water-based dyeing media.
Supercritical carbon hydroxide has been used with success in methods for dyeing synthetic fibres, for example, polyesters and polyamides, but the results of its use in the dyeing of natural fibres, for example, wool, cotton or silk fibres, have not been so satisfactory.
Disperse dyes, which are normally used for dyeing synthetic fibres, are in fact apolar and soluble in supercritical carbon dioxide, thus permitting vivid and fast dyeing of chemical fibres; these dyes do not, however, have an affinity to natural fibres which are essentially polar.
To obviate this incompatibility, it has been proposed (see, for example, M.L. Colombo et al . , "Treatments of cellulosic material with natural products dissolved in SCVF-C02" Proceeding of the 5th Meeting on Supercritical Fluid, March (1998) 357-360) to impregnate the natural fibres with bulking agents such as thiodiglycols and polyethylene glycols before the actual dyeing treatment, but without completely solving the problem. In fact, although this initially achieves a more satisfactory adhesion of the disperse dye to the fibres, the washings to which the fibres are subsequently subjected nevertheless bring about decolorization thereof .
The object of the present invention is therefore to provide a method of dyeing natural textile fibres with the use of a dyeing medium comprising supercritical carbon dioxide and a dye, which can ensure satisfactory and persistent adhesion of the dye to the fibres .
This object is achieved by means of a method of the type indicated at the beginning of the present description and characterized in that the dye is of the water-soluble, polar type, and in that the dyeing medium also comprises a polar co-solvent .
By virtue of the use of the polar co-solvent, polar dyes can be rendered soluble in supercritical carbon dioxide in which they would otherwise be insoluble, and can thus be brought into contact with the natural fibres for which they have a chemical affinity and on which they can effectively perform their dyeing action which is persistent over time and resistant to washing.
The co-solvent is preferably selected form the group consisting of methanol, ethanol, water and mixtures thereof.
The water-soluble polar dye is preferably of the reactive, direct, cationic, or acid type or the like.
The concentration of the co-solvent in the dyeing medium is advantageously between 2 and 20% and even more preferably between 5 and 10%. These concentrations, as well as all of those given in the remaining part of the present description, in the absence of any indication to the contrary, should be understood as molar concentrations relative to the moles of C02 in the working conditions .
The natural textile fibres which can be dyed by the method of the invention are of substantially any nature, for example, fibres and hair of animal origin, vegetable fibres, and mixtures thereof, particularly wool, cotton and silk fibres .
The general parameters of the dyeing method of the invention are preferably between 70 and 250 bars with regard to pressure, and between 50 and 120°C with regard to temperature .
Further advantages and characteristics of the present invention will become clear from the following examples provided by way of non-limiting indication.
EXAMPLE 1
Dyeing tests were performed in a 1 litre autoclave with a stirrer on samples in the form of small skeins of wool each weighing about 2 g, with a dyeing medium comprising: supercritical C0 , ethanol as a co-solvent at a molar concentration of about 10% relative to the C02, and a quantity of about 1 g, or in any case such as to ensure saturation of the dye bath, of a reactive dye.
The dyeing was carried out for about 2 hours at a pressure of about 200 bars and a temperature of about 90°C. Upon completion of this operation, the autoclave was emptied by depressurization in a single step. The dyed samples were then subjected to rapid washing in running water. The dyed samples had good colour intensity, good colour- fastness upon washing, and good light-fastness values.
EXAMPLE 2
The tests relating to this example were performed in conditions similar to those of Example 1, with the difference that skeins of cotton were dyed with a direct dye and at about 70°C.
The dyed samples had good colour intensity, reasonable colour-fastness upon washing, and good light-fastness values .
EXAMPLE 3
The tests relating to this example were carried out in similar conditions to those of Example 1 with the difference that a skein of silk was dyed. Moreover, whereas in some tests the same co-solvent was used as in Example 1, in others water at a molar concentration of 2% was used instead.
The dye samples had very good colour intensity, good colour- fastness upon washing, and good light-fastness values.
Naturally, the principle of the invention remaining the same, the details of construction and forms of embodiment may be varied widely with respect to those described purely by way of example, without thereby departing from its scope.

Claims

1. A method of dyeing natural textile fibres with the use of a dyeing medium comprising supercritical carbon dioxide and a dye, the method being characterized in that the dye is of the water-soluble, polar type, and in that the dyeing medium also comprises a polar co-solvent.
2. A method according to Claim 1, characterized in that the co-solvent is selected from the group consisting of methanol, ethanol, water and mixtures thereof.
3. A method according to any one of the preceding claims, characterized in that the dye is selected from the group consisting of reactive, direct, cationic and acid dyes.
4. A method according to any one of the preceding claims, characterized in that the molar concentration of the co- solvent in the dyeing medium is between 2 and 20% and preferably between 5 and 10%.
5. A method according to any one of the preceding claims, characterized in that the natural textile fibres are selected from the group consisting of fibres and hair of animal origin, vegetable fibres, and mixtures thereof.
6. A method according to any one of the preceding claims, characterized in that it is carried out at a pressure of between 70 and 250 bars.
7. A method according to any one of the preceding claims, characterized in that it is carried out at a temperature of between 50 and 120°C.
PCT/EP2000/006414 1999-07-09 2000-07-06 A method of dyeing natural textile fibres with a dyeing medium comprising supercritical carbon dioxide WO2001004410A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68224/00A AU6822400A (en) 1999-07-09 2000-07-06 A method of dyeing natural textile fibres with a dyeing medium comprising supercritical carbon dioxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITTO990598 IT1307050B1 (en) 1999-07-09 1999-07-09 DYEING PROCESS OF NATURAL TEXTILE FIBERS WITH A HALF DYEING INCLUDING SUPERCRITICAL CARBON DIOXIDE.
ITTO99A000598 1999-07-09

Publications (1)

Publication Number Publication Date
WO2001004410A1 true WO2001004410A1 (en) 2001-01-18

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Country Status (3)

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AU (1) AU6822400A (en)
IT (1) IT1307050B1 (en)
WO (1) WO2001004410A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6676710B2 (en) 2000-10-18 2004-01-13 North Carolina State University Process for treating textile substrates
WO2006049503A3 (en) * 2004-11-04 2006-08-31 Feyecon Dev & Implementation A method of dyeing a substrate with a reactive dyestuff in supercritical or near supercritical carbon dioxide
US8439982B2 (en) 2010-08-27 2013-05-14 Empire Technology Development Llc Dyeing of fibers using supercritical carbon dioxide and electrophoresis
CN106835558A (en) * 2016-11-21 2017-06-13 大连工业大学 A kind of anhydrous the boiling of supercritical carbon dioxide fluid bleachinges and dyeing integration apparatus
CN114592365A (en) * 2022-03-25 2022-06-07 青岛即发集团股份有限公司 Supercritical carbon dioxide fluid dyeing method with high disperse dye uptake

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3906724A1 (en) * 1989-03-03 1990-09-13 Deutsches Textilforschzentrum Dyeing process
GB2259525A (en) * 1991-09-11 1993-03-17 Ciba Geigy Ag Process for dyeing cellulosic textile material with disperse dyes
DE4404839A1 (en) * 1994-02-16 1995-08-17 Deutsches Textilforschzentrum Coating or impregnating substrates with polar cpds., esp. dyes
US6010542A (en) * 1997-08-29 2000-01-04 Micell Technologies, Inc. Method of dyeing substrates in carbon dioxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3906724A1 (en) * 1989-03-03 1990-09-13 Deutsches Textilforschzentrum Dyeing process
GB2259525A (en) * 1991-09-11 1993-03-17 Ciba Geigy Ag Process for dyeing cellulosic textile material with disperse dyes
DE4404839A1 (en) * 1994-02-16 1995-08-17 Deutsches Textilforschzentrum Coating or impregnating substrates with polar cpds., esp. dyes
US6010542A (en) * 1997-08-29 2000-01-04 Micell Technologies, Inc. Method of dyeing substrates in carbon dioxide

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6676710B2 (en) 2000-10-18 2004-01-13 North Carolina State University Process for treating textile substrates
WO2006049503A3 (en) * 2004-11-04 2006-08-31 Feyecon Dev & Implementation A method of dyeing a substrate with a reactive dyestuff in supercritical or near supercritical carbon dioxide
US7938865B2 (en) 2004-11-04 2011-05-10 Feyecon Development & Implementation B.V. Method of dyeing a substrate with a reactive dyestuff in supercritical or near supercritical carbon dioxide
US8439982B2 (en) 2010-08-27 2013-05-14 Empire Technology Development Llc Dyeing of fibers using supercritical carbon dioxide and electrophoresis
CN106835558A (en) * 2016-11-21 2017-06-13 大连工业大学 A kind of anhydrous the boiling of supercritical carbon dioxide fluid bleachinges and dyeing integration apparatus
CN106835558B (en) * 2016-11-21 2019-08-16 大连工业大学 A kind of supercritical carbon dioxide fluid bleachinges and dyeing integration apparatus without boiling
CN114592365A (en) * 2022-03-25 2022-06-07 青岛即发集团股份有限公司 Supercritical carbon dioxide fluid dyeing method with high disperse dye uptake
CN114592365B (en) * 2022-03-25 2023-04-07 青岛即发集团股份有限公司 Supercritical carbon dioxide fluid dyeing method with high disperse dye uptake

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Publication number Publication date
ITTO990598A1 (en) 2001-01-09
AU6822400A (en) 2001-01-30
IT1307050B1 (en) 2001-10-23

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