CN108797153B - Functional dyeing method based on eutectic solvent - Google Patents
Functional dyeing method based on eutectic solvent Download PDFInfo
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- CN108797153B CN108797153B CN201810647141.0A CN201810647141A CN108797153B CN 108797153 B CN108797153 B CN 108797153B CN 201810647141 A CN201810647141 A CN 201810647141A CN 108797153 B CN108797153 B CN 108797153B
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- 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
- D06P1/16—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 dispersed, e.g. acetate, dyestuffs
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
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- 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
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- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
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- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
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- 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
- D06P1/642—Compounds containing nitrogen
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- D06P1/655—Compounds containing ammonium groups
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- D06P1/908—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 organic solvents or aqueous emulsions thereof using specified dyes
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- D06P1/92—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 organic solvents or aqueous emulsions thereof in organic solvents
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- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
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- D06P2001/906—Solvents other than hydrocarbons
Abstract
The invention discloses a functional dyeing method based on a eutectic solvent, which is characterized in that a hydrogen bond acceptor compound and a hydrogen bond donor compound capable of photoinitiating polymerization are uniformly mixed to prepare the eutectic solvent, and a disperse dye is added and stirred to be dissolved to prepare a pre-dyeing solution; adding a photo-initiated polymerization agent into the pre-dyeing solution, and stirring and dissolving to obtain a dyeing solution; and dyeing the fabric to be dyed by using the dye solution, and irradiating the pre-dyed fabric by using ultraviolet light to obtain the dyed fabric. The invention adopts green and novel eutectic solvent as the functional printing and dyeing medium of the disperse dye, and utilizes the existing fabric dyeing equipment to directly carry out treatment so as to fix the disperse dye on the fabric. The invention, as a functional dyeing technology, has the advantages of environmental protection, no pollution, low wastewater discharge, low price, convenient operation, suitability for industrial production and the like.
Description
Technical Field
The invention relates to a functional dyeing method based on a eutectic solvent, and belongs to the field of dyeing and after-finishing of textiles.
Background
Disperse dyes were made available as early as the beginning of the 20 th century, when primarily intended for the dyeing of acetate fibers. With the subsequent rapid development of synthetic fibers, disperse dyes became one of the fastest growing dyes. The main methods for dyeing the disperse dye are a carrier dyeing method, a high-temperature high-pressure dyeing method and a hot-melt dyeing method, and because the solubility of the disperse dye in water is poor, auxiliary agents which are difficult to biodegrade, such as a dispersing agent, are required to be added for assisting dyeing, so that the pollution to the environment is very obvious. In addition, with the increasing severity of ecological environment problems, the waste water problems caused by disperse dyes become more prominent, and the difficulty of waste water treatment is increased by a large amount of dispersing agents contained in dyeing residual liquid and dyes which cannot be recovered in reduction cleaning liquid.
Organic solvent dyeing is considered as a green and environment-friendly dyeing technology which can reduce the discharge of printing and dyeing wastewater. However, in the case of trichloroethylene or tetrachloroethylene solvent dyeing which has been studied in many cases, the technique has not been developed further because the dye uptake of the disperse dye is low due to its excessively high solubility in trichloroethylene or tetrachloroethylene and a halogenated hydrocarbon solvent which is harmful to health may remain on the dyed fabric.
The chemical fiber textile products dyed by the disperse dyes have bright colors and excellent washing fastness, but due to the influence of the structures of the disperse dyes, the dyeing process and the like, the disperse dyes are only mainly used for dyeing and printing synthetic fibers such as polyester fibers and the like at present, so that the application of the disperse dyes is greatly limited. In order to expand the application of disperse dyes, the most widely used method is pigment printing, because pigment printing has no requirement on the selectivity of dyes and fabrics, and is suitable for textiles made of any fiber, and the fixed dyeing effect is achieved through the adhesion effect of paint on the fabrics.
Therefore, the methods have certain limitations in application, and the consumption of the disperse dye in the dyeing of the polyester fiber is very large, so that the generated printing and dyeing wastewater is very high. Therefore, it is very important to develop a dyeing technology which has simple process, good dyeing effect, less wastewater discharge and is suitable for more types of fibers.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method is characterized in that the functional dyeing method based on the eutectic solvent is provided, and direct dyeing can be realized on the basis of the existing fabric dyeing equipment, so that equipment is not added, and the cost is not increased; the raw materials used are low in cost, have good chemical and physical stability, are green and pollution-free, and are suitable for industrial production.
In order to solve the above problems, the present invention provides a functional dyeing method based on a eutectic solvent, which is characterized by comprising the steps of:
step 1): uniformly mixing a hydrogen bond acceptor compound and a hydrogen bond donor compound capable of carrying out photoinitiated polymerization, heating at 80-100 ℃ for 2-4 hours to prepare a eutectic solvent, adding a disperse dye into the eutectic solvent, and stirring and dissolving to prepare a pre-dyeing solution;
step 2): adding a photo-initiated polymerization agent into the pre-dyeing solution, and stirring and dissolving to obtain a dyeing solution;
step 3): dyeing the fabric to be dyed by using a dye solution, irradiating the pre-dyed fabric for 10 s-3 min by using ultraviolet light, drying the pre-dyed fabric for 30-60 min at the temperature of 100-.
Preferably, the hydrogen bond acceptor compound in the step 1) is at least one of choline, betaine, and amino acid; the hydrogen bond donor compound capable of photo-initiated polymerization is at least one of maleic acid, fumaric acid, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl-methacrylamide, N-ethylacrylamide, N-methylolacrylamide, N-methylol-methacrylamide, and N-hydroxyethylacrylamide.
Preferably, the molar ratio of the hydrogen bond acceptor compound to the hydrogen bond donor compound capable of photoinitiated polymerization in the step 1) is (1-3) to (1-6).
More preferably, the molar ratio of the hydrogen bond acceptor compound to the photo-initiated polymerizable hydrogen bond donor compound is 1: 2.
More preferably, the choline is at least one of choline chloride and choline bromide; the betaine is at least one of betaine and betaine hydrochloride; the amino acid is at least one of glycine, alanine and glutamic acid; the disperse dye is at least one of c.i. disperse red 54, 60, 73, 74, 153, 167, 177, c.i. disperse yellow 64, 54, 104, 211, and c.i. disperse blue 56, 60, 79.
Preferably, the disperse dye in the step 1) is a conventional pure disperse dye without adding a dispersant; the addition amount of the disperse dye is 1-20 g/L (eutectic solvent).
Preferably, the photoinitiated polymerizer in the step 2) is azodiisobutyramidine hydrochloride V-50, azodiisopropyl imidazoline hydrochloride VA-044, benzoin dimethyl ether, 2-dimethoxy-2-phenyl acetophenone, 2, 4-dialkyl thioxanthone, Norrish type II photoinitiator or Norrish type I photoinitiator.
Preferably, the addition amount of the photo-initiation polymerization agent in the step 2) is 0.05-1% of the mass of the hydrogen bond donor compound capable of photo-initiation polymerization.
Preferably, the fabric to be dyed in the step 3) is a natural fiber fabric, a synthetic fiber fabric or a blended fabric of the natural fiber fabric and the synthetic fiber fabric.
Preferably, the ultraviolet light in the step 3) is generated by an ultraviolet lamp of 100-800W, and the light intensity range is 0.01-3 mW/cm2The dominant wavelength is 254nm or 365 nm.
The pre-dyeing solution prepared by dissolving the disperse dye by the eutectic solvent has stable performance and can be stored for a long time in a dark place. The invention can also be applied to other dyes which are soluble in the eutectic solvent and do not react with the hydrogen bond acceptor compound or the hydrogen bond donor compound, and the prepared dyed fabric also has the performances of antibiosis, antistatic, electric conduction or wrinkle resistance and the like.
The eutectic solvent is used as a medium of the disperse dye for dyeing or printing natural fiber fabrics, and is different from an adhesive, a cross-linking agent and a color fixing agent in the general sense. The eutectic solvent is not only low-viscosity liquid, but also low-viscosity liquid before the polymerization condition is initiated after the disperse dye is dissolved, so that the fabric can be finished by using conventional printing and dyeing equipment, and the low-viscosity liquid is uniformly distributed on the surface of the fabric after finishing; the hydrogen bond donor compound which can be polymerized by light initiation in the eutectic solvent can be rapidly polymerized into a film after polymerization initiation, so that the effects of preventing dye particles from aggregating, printing and dyeing without flaws and the like can be achieved, and the fabric has better hand feeling. The hydrogen bond acceptor compound in the eutectic solvent has the effects of conductivity, antibiosis and the like, and the hydrogen bond donor compound which can be polymerized by light initiation can also enable the cotton fabric to generate the crease-resistant effect after polymerization, so that the method can dye the fabric and endow the fabric with the characteristics of antibiosis, conductivity (antistatic), crease resistance and the like, the effect of functional finishing of the fabric can be achieved in the printing and dyeing process, and the additional value of the fabric is greatly increased.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method utilizes the prior fabric dyeing equipment to dye directly, does not add equipment or increase cost, is applied to green and environment-friendly production in the textile industry, and can be produced in large quantities;
(2) different from a common dyeing method, the disperse dye can be dissolved in a eutectic solvent, and the conditions of dye particle aggregation and the like can not occur, so that the printing and dyeing effect is more uniform, the printing and dyeing defects are reduced, and the hand feeling is better;
(3) the hydrogen bond donor compound which can be polymerized by light initiation in the eutectic solvent can form a film through a crosslinking reaction, so that the dye can be fixed on the fabric by the polymerization film for a long time, and the fastness to washing is high;
(4) the pre-dyeing solution prepared by dissolving the disperse dye by the eutectic solvent has stable performance and can be stored for a long time in a dark place;
(5) the eutectic solvent used in the method is low-viscosity liquid before ultraviolet light-initiated polymerization, and can be used for treating fabrics in dip dyeing, pad dyeing or printing modes, so that the operation is convenient; after the polymerization is initiated by ultraviolet light, the polymerization speed is high, so the polymerization initiation time and mode can be flexibly applied according to the product design;
(6) the invention dyes the fabric, also performs functional finishing on the fabric, endows the fabric with performances of antibiosis, conductivity (antistatic) and the like by utilizing the hydrogen bond acceptor compound with antibacterial property in the eutectic solvent, and endows the fabric with crease-resistance performance by polymerizing the hydrogen bond donor compound into a film;
(7) the prepared eutectic solvent is non-toxic and biodegradable, reduces the difficulty and resource investment of waste liquid treatment, reduces the waste of water resources and the discharge of printing and dyeing wastewater, and is suitable for industrial production;
(8) the present invention can be applied to various types of fabrics.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
Mixing choline chloride and acrylic acid in a molar ratio of 1: 2 to prepare a eutectic solvent; ultrasonically dissolving disperse red 73 dye in a eutectic solvent, preparing a pre-dyeing solution with the concentration of 4g/L, and storing in a dark place; during dyeing, 2-dimethoxy-2-phenylacetophenone is added into the pre-dyeing solution as a polymerization initiator, and the using amount of the polymerization initiator is 0.5 percent of the mass of acrylic acid; the pre-dyeing liquid is used for carrying out two-dipping and two-rolling on the polyester fabric, and ultraviolet (300W ultraviolet lamp, light intensity range is 1 mW/cm)2Main wavelength of the generated ultraviolet light is 254nm) for 20s, drying for 45 minutes at 100 ℃, washing and airing to obtain the dyed fabric.
The K/S value of the dyed fabric is 15, and the surface specific resistance of the dyed polyester fabric is 4 × 105Ohms, antistatic effect is good, and the bacteriostasis rate to escherichia coli and staphylococcus aureus is more than 99%. The fastness to washing of the dyed fabric is 4-5 grade, the fastness to dry rubbing is 4-0 grade, and the fastness to wet rubbing is 4-0 grade.
Example 2
Mixing choline chloride and acrylamide according to a molar ratio of 1: 2 to prepare a eutectic solvent; ultrasonically dissolving disperse blue 56 dye in a eutectic solvent, preparing a pre-dyeing solution with the concentration of 18g/L, and storing in a dark place; during dyeing, adding azodiisobutyl amidine hydrochloride V-50 serving as a polymerization initiator into a pre-dyeing solution, wherein the using amount of the azodiisobutyl amidine hydrochloride is 0.5 percent of the mass of acrylamide; carrying out three-dipping and three-rolling on the cotton fabric by the pre-dyeing liquid, wherein the soaking time is 5 minutes; ultraviolet (300W ultraviolet lamp, light intensity range is 1.5 mW/cm)2The dominant wavelength of the generated ultraviolet light is 254nm) for 20s so that the eutectic solvent has polymerization and crosslinking reaction, drying for 60 minutes at 100 ℃, washing and airing to obtain the dyed fabric.
The K/S value of the dyed fabric is 20, the crease recovery angle of the dyed cotton fabric is 200 degrees, and the bacteriostasis rate to escherichia coli and staphylococcus aureus is more than 99 percent. The obtained dyed fabric has washing fastness of 4-5 grade, dry rubbing fastness of 4-0 grade and wet rubbing fastness of 4-0 grade.
Example 3
Mixing betaine and acrylamide at a molar ratio of 1: 2A eutectic solvent; ultrasonically dissolving disperse yellow 64 dye in a eutectic solvent, preparing a pre-dyeing solution with the concentration of 8g/L, and storing in a dark place; during dyeing, adding azodiisopropyl imidazoline hydrochloride VA-044 serving as a polymerization initiator into a pre-dyeing solution, wherein the dosage of the azodiisopropyl imidazoline hydrochloride is 0.6 percent of the mass of acrylamide; carrying out three-dipping and three-rolling on the chinlon fabric by using the pre-dyeing liquid; ultraviolet (100W ultraviolet lamp, light intensity range is 0.5 mW/cm)2The dominant wavelength of the generated ultraviolet light is 365nm) for 40s, drying for 30 minutes at 120 ℃, washing and airing to obtain the dyed fabric.
The K/S value of the dyed fabric is 15, and the surface specific resistance of the dyed nylon fabric is 9 × 107And Ohms, the bacteriostasis rate of the antibacterial agent to escherichia coli and staphylococcus aureus is more than 99%. The washing fastness of the dyed fabric is 4-5 grade, the dry rubbing fastness is 4-0 grade, and the wet rubbing fastness is 4-0 grade.
Example 4
Mixing betaine and methacrylamide according to the molar ratio of 1: 2 to prepare a eutectic solvent; ultrasonically dissolving disperse red 74 dye in a eutectic solvent, preparing a pre-dyeing solution with the concentration of 10g/L, and storing in a dark place; during dyeing, adding a Norrish II type photoinitiator into a pre-dyeing solution as a polymerization initiator, wherein the dosage of the Norrish II type photoinitiator is 0.6 percent of the mass of methacrylamide; carrying out three-dipping and three-rolling on the cotton fabric by the pre-dyeing liquid; ultraviolet (500W ultraviolet lamp, light intensity range is 2 mW/cm)2And the dominant wavelength of the generated ultraviolet light is 365nm) for 15s, drying for 45 minutes at 110 ℃, washing and airing to obtain the dyed fabric.
The K/S value of the dyed fabric is 15, the crease recovery angle of the dyed cotton fabric is 200 degrees, and the bacteriostasis rate to escherichia coli and staphylococcus aureus is more than 99 percent. The washing fastness of the dyed fabric is 4-5 grade, the dry rubbing fastness is 4-0 grade, and the wet rubbing fastness is 4-0 grade.
Example 5
Mixing glycine and N-hydroxymethyl acrylamide in a molar ratio of 1: 3 to prepare a eutectic solvent; ultrasonically dissolving disperse red 177 dye into a eutectic solvent, preparing a pre-dyeing solution with the concentration of 12g/L, and storing in a dark place; during dyeing, 2-dimethoxy-2-phenylacetophenone is added into the pre-dyeing solution as a polymerization initiator, and the dosage of the polymerization initiator is 1 mass of N-hydroxymethyl acrylamidePercent; carrying out two-dipping and two-rolling on the cotton fabric by the pre-dyeing liquid; ultraviolet (800W ultraviolet lamp, light intensity range is 3 mW/cm)2Main wavelength of the generated ultraviolet light is 254nm) for 10s, drying for 30 minutes at 120 ℃, washing and airing to obtain the dyed fabric.
The K/S value of the dyed fabric is 16, the crease recovery angle of the dyed cotton fabric is 200 degrees, and the bacteriostasis rate to escherichia coli and staphylococcus aureus is more than 99 percent. The washing fastness of the dyed fabric is 4-5 grade, the dry rubbing fastness is 4-0 grade, and the wet rubbing fastness is 4-0 grade.
Example 6
Mixing choline chloride and N-hydroxymethyl-methacrylamide in a molar ratio of 1: 2 to prepare a eutectic solvent; ultrasonically dissolving disperse blue 79 dye in a eutectic solvent, preparing a pre-dyeing solution with the concentration of 10g/L, and storing in a dark place; during dyeing, adding azodiisobutyl amidine hydrochloride V-50 serving as a polymerization initiator into a pre-dyeing solution, wherein the using amount of the azodiisobutyl amidine hydrochloride is 0.6 percent of the mass of N-hydroxymethyl-methacrylamide; carrying out three-dipping and three-rolling on the cotton fabric by the pre-dyeing liquid; ultraviolet (300W ultraviolet lamp, light intensity range is 1.5 mW/cm)2And the dominant wavelength of the generated ultraviolet light is 365nm) for 30s, drying for 60 minutes at 100 ℃, washing and airing to obtain the dyed fabric.
The K/S value of the dyed fabric is 15, the crease recovery angle of the dyed cotton fabric is 200 degrees, and the bacteriostasis rate to escherichia coli and staphylococcus aureus is more than 99 percent. The washing fastness of the dyed fabric is 4-5 grade, the dry rubbing fastness is 4-0 grade, and the wet rubbing fastness is 4-0 grade.
Claims (9)
1. A functional dyeing method based on a eutectic solvent is characterized by comprising the following steps:
step 1): uniformly mixing a hydrogen bond acceptor compound and a hydrogen bond donor compound capable of carrying out photoinitiated polymerization, heating at 80-100 ℃ for 2-4 hours to prepare a eutectic solvent, adding a disperse dye into the eutectic solvent, and stirring and dissolving to prepare a pre-dyeing solution;
step 2): adding a photo-initiated polymerization agent into the pre-dyeing solution, and stirring and dissolving to obtain a dyeing solution;
step 3): dyeing a fabric to be dyed by using a dye solution, irradiating the pre-dyed fabric for 10 s-3 min by using ultraviolet light, drying the pre-dyed fabric for 30-60 min at the temperature of 100-;
the hydrogen bond receptor compound in the step 1) is at least one of choline, betaine and amino acid; the hydrogen bond donor compound capable of photoinitiated polymerization is at least one of maleic acid, fumaric acid, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl-methacrylamide, N-ethylacrylamide, N-methylolacrylamide, N-methylol-methacrylamide and N-hydroxyethylacrylamide; the disperse dye is at least one of c.i. disperse red 54, 60, 73, 74, 153, 167, 177, c.i. disperse yellow 64, 54, 104, 211, and c.i. disperse blue 56, 60, 79.
2. The functional dyeing method based on the eutectic solvent according to claim 1, characterized in that the molar ratio of the hydrogen bond acceptor compound to the hydrogen bond donor compound capable of photoinitiated polymerization in the step 1) is (1-3): (1-6).
3. The functional dyeing method based on eutectic solvent according to claim 2, characterized in that the molar ratio of the hydrogen bond acceptor compound to the photo-initiated polymerizable hydrogen bond donor compound is 1: 2.
4. the functional dyeing method based on the eutectic solvent according to claim 1, characterized in that the choline is at least one of choline chloride and choline bromide; the amino acid is at least one of glycine, alanine and glutamic acid.
5. The functional dyeing method based on a eutectic solvent according to claim 1, wherein the disperse dye in the step 1) is a conventional pure disperse dye to which no dispersant is added; the addition amount of the disperse dye is 1-20 g/L, and the gram weight of the disperse dye is determined relative to each liter of eutectic solvent.
6. The functional dyeing method based on eutectic solvent according to claim 1, characterized in that the photo-initiated polymerization agent in step 2) is azobisisobutyramidine hydrochloride V-50, azobisisopropylimidazoline hydrochloride VA-044, benzoin dimethyl ether, 2-dimethoxy-2-phenylacetophenone, 2, 4-dialkylthioxanthone, Norrish type ii photo-initiator or Norrish type i photo-initiator.
7. The functional dyeing method based on the eutectic solvent according to claim 1, wherein the addition amount of the photo-initiated polymerization agent in the step 2) is 0.05 to 1% of the amount of the photo-initiated polymerizable hydrogen bond donor compound.
8. The functional dyeing method based on eutectic solvent according to claim 1, characterized in that the fabric to be dyed in step 3) is a natural fiber fabric, a synthetic fiber fabric or a blend of the two.
9. The functional dyeing method based on eutectic solvent according to claim 1, characterized in that the ultraviolet light in step 3) is generated by an ultraviolet lamp of 100-800W, and the light intensity is in the range of 0.01-3 mW/cm2The dominant wavelength is 254nm or 365 nm.
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| CN112813708B (en) * | 2021-02-20 | 2021-10-22 | 江南大学 | Salt-free less-water circulating dyeing method for cellulose textile reactive dye |
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