WO2020077665A1 - 一种混合流体介质的无水纤染方法 - Google Patents

一种混合流体介质的无水纤染方法 Download PDF

Info

Publication number
WO2020077665A1
WO2020077665A1 PCT/CN2018/111893 CN2018111893W WO2020077665A1 WO 2020077665 A1 WO2020077665 A1 WO 2020077665A1 CN 2018111893 W CN2018111893 W CN 2018111893W WO 2020077665 A1 WO2020077665 A1 WO 2020077665A1
Authority
WO
WIPO (PCT)
Prior art keywords
dyeing
fluid medium
mixed fluid
fibers
anhydrous
Prior art date
Application number
PCT/CN2018/111893
Other languages
English (en)
French (fr)
Inventor
龙家杰
蔡冲
Original Assignee
苏州大学
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 苏州大学 filed Critical 苏州大学
Priority to US16/346,227 priority Critical patent/US11560669B2/en
Publication of WO2020077665A1 publication Critical patent/WO2020077665A1/zh

Links

Images

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
    • D06P1/0004—General aspects of dyeing
    • D06P1/0016—Dye baths containing a dyeing agent in a special form such as for instance in melted or solid form, as a floating film or gel, spray or aerosol, or atomised 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
    • D06P1/0004—General aspects of dyeing
    • 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
    • D06P1/16—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
    • 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
    • D06P1/38—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 reactive 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
    • D06P1/90—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
    • 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
    • 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
    • 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
    • D06P2001/0084—Non-aqueous dyeing in an inorganic medium
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the invention relates to the technical field of textile dyeing and finishing, in particular to a method for dyeing anhydrous fibers in a mixed fluid medium.
  • supercritical fluid technology has developed from pure basic theory and laboratory research to practical applications. And has been rapidly improved and expanded in many fields, such as supercritical fluid anhydrous dyeing, supercritical fluid extraction, supercritical fluid chemical reaction, supercritical fluid cleaning technology, etc. Because the critical temperature and critical pressure conditions of carbon dioxide are relatively mild (31.1 °C and 7.38MPa), and have the characteristics of non-toxic, non-flammable, non-explosive, etc., it has become the most widely used supercritical fluid medium today.
  • Supercritical CO 2 fluid has both high permeability and low viscosity equivalent to gas, but also has a density close to that of liquid and excellent dissolving ability for non-polar substances. Therefore, it can dissolve non-polar or weak polar dyes like liquids, and it can also penetrate dissolved fibers like fibers to achieve the purpose of dyeing.
  • the supercritical CO 2 fluid replaces water as the dyeing medium.
  • the basic theoretical basis is to use the similar compatibility principle to dissolve suitable dyes in a single molecule state in the fluid medium, and then carry the supercritical CO 2 fluid with the dye to the fiber surface. Mass transfer occurs, which causes the dye molecules to adsorb and dye, and further diffuses and fixes inside the fiber with the fluid, thereby reaching the purpose of dyeing.
  • the structure is relatively simple, the molecular mass is small, and the less polar dye is easy to dissolve in the supercritical CO 2 fluid. Therefore, in the dyeing process using supercritical carbon dioxide fluid as the medium, generally, hydrophobic disperse dyes with smaller molecules and weaker polarities are used more often.
  • synthetic fibers such as polyester are also hydrophobic, they are easy to expand in supercritical carbon dioxide fluid, so synthetic fibers can obtain excellent dyeing effects. So far, most synthetic fibers, such as polyester, are dyed with disperse dyes in supercritical carbon dioxide fluids, which can meet commercial standards.
  • the supercritical CO 2 fluid medium has a low polarity and cannot be well dissolved or almost incompatible with high-polarity water-soluble dyes; while the ordinary disperse dyes dissolved in the supercritical CO 2 fluid have a simple molecular structure due to their small molecular weight , It has low affinity or directness to natural fibers, and cannot obtain good dyeing depth and color fastness, so it can not really achieve good dyeing of various types of natural fibers. More importantly, the hydrophobic carbon dioxide fluid cannot effectively expand natural fibers in a dry state, and cannot provide the necessary conditions for the dyeing of dye molecules, especially diffusion. Therefore, it is of great significance to solve the problem of dyeing natural fibers in supercritical CO 2 fluid.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and to provide an anhydrous fiber dyeing method using a mixed fluid medium.
  • Its main content is: the supercritical carbon dioxide fluid medium and certain conditions A certain proportion of steam is mixed to form a mixed fluid, which is used as a processing medium for anhydrous dyeing.
  • the steam is used to improve the polarity of the supercritical CO 2 fluid medium, so as to increase the solubility of the dye in the mixed fluid medium, and at the same time, the steam also serves to expand the natural fibers in the dry state, which is used for the adsorption of the dye Dyeing provides the necessary conditions.
  • the dry fibers may be staple fibers such as cotton or natural hemp loose fibers after processing, or synthetic fibers such as viscose and polyester , Nylon, acrylic staple fiber processed.
  • the mechanical compaction method is to perform a uniform and uniform layer-by-layer extrusion process on the fluffy fibers by the action of mechanical external force, so that it can be smoothly packed according to a certain tightness.
  • layer-by-layer extrusion processing the density of fibers is more uniform, which helps to improve the uniformity of dyeing.
  • step (1) in the step (1), when the dry fiber is “stepped on cotton” in the sarong in a layered form, its certain tightness is 50-300 kg / m 3 .
  • the specially-made porous yarn cage is made of Teflon-coated or other non-conductive thermal surface materials, and hollow series of small holes are distributed around the yarn cage and on the central hollow tube .
  • the temperature in the dyeing tank often exceeds 100 ° C.
  • the Teflon or non-conductive thermal surface material can reduce the heat transferred to the fibers in the yarn cage to avoid damage to the fibers.
  • the suitable non-carbon dioxide medium in step (2) may be one or more of saturated steam, superheated steam, and other polar solvents.
  • the polar solvent may be methanol, ethanol, acetone or the like.
  • step (2) a certain pressure and time are processed, the pressure is 0-1 Mpa, and the time is 5 to 180 min.
  • the special dye in the dissolved state is a reactive disperse dye whose reactive group is one or more of vinyl sulfone, vinyl, mesitazine type, and nicotinic acid structure, or Their derivative compounds.
  • the solvent for the dissolved special dye may be one or more of supercritical carbon dioxide, ethanol, acetone, methanol, and deionized water.
  • step (3) the ratio when the solvent used is two mixed solvents may be 1: 5 to 5: 1.
  • the mixed fluid is circulated in the dyeing system by the circulation pump, so that the dye molecules and the fibers are in full contact. More preferably, the fluid is in a state of dynamic and static circulation in the dyeing system, that is, after the fluid circulates for a certain period of time, the circulation pump is turned off to allow the fluid to stand for a certain period of time, then the circulation pump is started, and the above operation is repeated to make the fluid alternately in a dynamic and static state.
  • step (3) in the predetermined dyeing process, the temperature is 50-160 ° C, the pressure is 7-35Mpa, the dynamic and static circulation time ratio of the fluid is 1: 5-10: 1, and the processing time is 10 ⁇ 180min.
  • step (4) the process of online floating color cleaning under certain conditions is as follows: the temperature is 30-100 ° C, the pressure is 8-35Mpa, and the dynamic-static cycle time ratio of the fluid is 1: 5- 10: 1, the processing time is 10 ⁇ 120min.
  • step (4) after the dyeing is completed, the carbon dioxide is recovered by the circulation system for the next recycling, and at the same time, the carbon dioxide gas in the dyeing system is recovered to atmospheric pressure to realize the direct opening of the dyeing tank.
  • the technical solution of the present invention has the following remarkable features and advantages:
  • the supercritical carbon dioxide fluid medium is mixed with a certain proportion of steam under certain conditions to form a mixed fluid, which is used as a process for anhydrous dyeing medium.
  • the polarity of supercritical carbon dioxide fluid medium is improved, and the solubility of the dye in the mixed fluid medium is increased.
  • the effective swelling of dry natural fibers is also achieved, which provides the necessary conditions for dye adsorption and dyeing. Therefore, the technology of the present invention can effectively improve the dyeing performance of natural fibers. And its process is simple, without the use of traditional water bath, no dyeing wastewater is generated, the required process flow is short, and the efficiency is high.
  • the fiber can also be used to clean the fiber online to remove the floating color, so as to obtain a good quality dry fiber dyed product.
  • FIG. 1 is a schematic diagram of a system for dyeing fabric in supercritical carbon dioxide fluid provided by an example of the present invention.
  • Figure 1 1. CO 2 storage tank; 2 , 6, 9, 11, 11 ', 13, 14, 15, shut-off valve; 3. condenser; 4. booster pump; 5. preheater; 7. Dye dissolving unit; 8, filter; 10, fiber dyeing and dyeing cylinder; 12, circulation pump; 12 ', gas recovery pump; 15, fine adjustment valve; 16, 19, thermometer; 17, 20, pressure gauge; 18, separation kettle; 21. Purifier.
  • Figure 2 is a cross-sectional view of the dyeing tank, in which: 1, fluid and dye inlet; 2, non-CO 2 medium inlet shut-off valve; 3, porous yarn cage; 4, fluid outlet; 5, quick opening structure; 6, dyeing tank sealing cover; 7 , Non-CO 2 media outlet; 8, interface.
  • the short fibers used in this experimental example are pure cotton fibers, dry fibers that have not been treated before dyeing; the dyes used are supercritical CO 2 special active dispersion yellow and active dispersion red.
  • the steps of a method for dyeing an anhydrous fiber of a mixed fluid medium used in the embodiments of the present invention are as follows.
  • the dry fiber is mechanically compressed, and the special porous yarn cage is packed in a layered form with a certain degree of tightness (see the porous yarn cage in Figure 2), then the yarn cage is sealed and the dyeing cylinder sealing cover is closed.
  • Close the shut-off valves 9, 14 in the system open the non-CO 2 medium inlet shut-off valve 2, and pass a certain amount of saturated steam into the dyeing tank.
  • the pressurization system including the CO 2 storage tank 1, the condenser 3, the pressure pump 4, and the preheater 5 is started to pressurize the dyeing circulation system and preheat and heat the fluid, This effectively forms a mixed fluid medium and allows the dye in the dye dissolving unit 7 to be fully dissolved.
  • a predetermined temperature such as 120 ° C.
  • the pressure reaches a preset value, such as 20 MPa
  • the pressure pump 4 stops the pump, closes the shut-off valve 6, and starts the circulation pump 12 in the dyeing circulation circuit.
  • the dissolved dye is circulated with the formed mixed fluid, and fully dyed with the fiber to be dyed.
  • the ratio of the circulation time of the mixed fluid to the static time during the dyeing process is 5: 1.
  • the dissolved dye fully contacts the fibers in the porous sarong through its own molecular thermal motion and fluid mass transfer, and completes the adsorption, dyeing, diffusion, and fixation processes.
  • the fine adjustment valve 15 is opened to relieve the pressure of the system, and the dye and mixture in the dyeing circulation system are separated and recovered by a separation and recovery system composed of a gas recovery pump 12 ', a separation kettle 18, a purifier 21, a condenser 3 The fluid is separated and recovered.
  • the temperature is 30-100 °C
  • the pressure is 8-35Mpa
  • the dynamic and static cycle time ratio of the carbon dioxide fluid is 1: 5-10: 1
  • the surface color depth value (K / S) and color value (L *, a *, b *, C * and h °) of the water-fiber dyed samples in the mixed fluid medium were measured with the Hunterlab Ultrascan PRO spectrophotometer Determination. During the test, choose D 65 light source, 10 ° viewing angle, uniformly mix the fibers for sample preparation, each sample is randomly tested for 8 points, and finally calculate the arithmetic average.
  • the levelness of the fiber is determined by the standard deviation of the surface color depth value of the tested sample at the maximum absorption wavelength To measure, the calculation method is shown in (1).
  • the calculation method is shown in (2).
  • Table 1.1 and Table 1.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse yellow dye (omf is 5%).
  • the content of steam in the mixed fluid in the system is 2.5g / L, and 10ml of acetone is added to the dye dissolving unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa mixed fluid medium.
  • the mixed fluid static dyeing cycle is every 1min after 1min, the dyeing temperature is 120 °C, and the total dyeing time is 60min.
  • the supercritical CO 2 fluid floatation cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the fluid static dyeing is circulated for 1min after every 5min
  • the total cleaning time is 30min.
  • Table 1.1 show that the active dispersed yellow is used as the dye, and the mixed fluid anhydrous fiber dyeing method of the present invention can obtain a good dyeing effect on dry cotton fibers.
  • the hue angle h ° of the anhydrous fiber dyed sample of Example 1 is 88.30, and its yellow shade is more pure and the color is more vivid.
  • Table 1.1 also shows that the standard deviation of the color depth value of the sample surface of Example 1 is small, The value is 0.045, indicating that the sample of Example 1 has excellent levelness.
  • Table 1.2 shows that the conventional color fastness of the sample of Example 1 is better, and the fade level is 3-4.
  • the color fastness to acrylic, polyester and acetate can reach level 4 or above.
  • the color fastness of nylon is also 3-4.
  • Table 2.1 and Table 2.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse yellow dye (omf is 5%).
  • the content of steam in the mixed fluid in the system is 2.5 g / L, and 10 ml of methanol is added to the dye dissolving unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa mixed fluid medium.
  • the mixed fluid static dyeing cycle is every 1min after 1min, the dyeing temperature is 120 °C, and the total dyeing time is 60min.
  • the supercritical CO 2 fluid floatation cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the fluid static dyeing is circulated for 1min after every 5min
  • the total cleaning time is 30min.
  • the related experimental results in Table 2.1 show that the active dispersion yellow is used as the dye, and the mixed fluid anhydrous fiber dyeing method of the present invention can obtain a good dyeing effect on dry cotton fibers.
  • the hue angle h ° of the sample of Example 2 is 84.97, and its yellow shade is more pure, the color is more vivid, and the C * value is increased to 23.23.
  • the sample of Example 2 is also under the same large proportion of fluid conditions, and its surface color depth value It can also reach 1.280, which also proves that the sample of Example 2 has good dyeing and fixing properties.
  • Table 2.1 also shows that the standard deviation of the surface color depth value of the sample of Example 2 is also small. The value is 0.022, indicating that the inventive technique has excellent levelness on the sample of Example 2.
  • Table 2.2 shows that the conventional color fastness of the sample of Example 2 is also good, and its fading level is 3-4.
  • the color fastness to cotton, sheep wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good.
  • Table 3.1 and Table 3.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse yellow dye (omf is 2%).
  • the steam content in the mixed fluid in the system is 5g / L, and 15ml of acetone is added to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa of mixed fluid.
  • the mixed fluid static dyeing cycle is 1min every 5min, the dyeing temperature is 130 °C, and the total dyeing time is 40min.
  • the supercritical CO 2 fluid floatation cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the fluid static dyeing is circulated for 1min after every 5min
  • the total cleaning time is 30min.
  • Example 3 is also carried out under the same large proportion of fluid conditions, and the surface color depth value of the sample It can also reach 0.949, which also proves that under the conditions of Example 3, the special dye has good dyeing and fixing properties on dry cotton fibers.
  • Table 3.1 also shows that the standard deviation of the color depth value of the sample surface is also small under this experimental condition. The value is 0.020, indicating that the mixed fluid anhydrous fiber dyed sample in Example 3 is also excellent in levelness.
  • Table 3.2 shows that the conventional color fastness of the sample in Example 3 is also good, and its color fastness reaches grade 4.
  • the color fastness to cotton, wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good.
  • Table 4.1 and Table 4.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse red dye (omf is 2%).
  • the steam content in the mixed fluid in the system is 5g / L, and 15ml of acetone is added to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa of mixed fluid.
  • the mixed fluid static dyeing cycle is 1min every 5min, the dyeing temperature is 130 °C, and the total dyeing time is 40min.
  • the supercritical CO 2 fluid floatation cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the fluid static dyeing is circulated for 1min after every 5min
  • the total cleaning time is 30min.
  • Table 4.1 show that, using the mixed fluid anhydrous fiber dyeing method of the present invention, the reactive disperse red dye can achieve good dyeing effect on dry cotton fibers.
  • the hue angle of the sample is 4.36, the chromaticity index b * value is small, and the red color light is relatively pure. Its C * value is 15.01, and its color is more vivid.
  • the surface color depth value It can also reach 0.954, which also proves that the special dye has good dyeing and fixing properties on dry cotton fibers under the mixed fluid anhydrous fiber dyeing conditions of Example 4.
  • Table 4.1 also shows that the standard deviation of the surface color depth value of this sample is also small. The value is 0.051, indicating that the level dyeing property of the mixed fluid anhydrous fiber dyed sample in Example 4 is also very good.
  • Table 4.2 shows that with the mixed fluid anhydrous fiber dyeing method of the present invention, the conventional color fastness of the samples is also excellent. Its fading fastness can reach level 4. The color fastness to cotton, wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good. Therefore, the above results show that, under the condition of selecting active disperse red dyed dry cotton fibers, a good anhydrous dyeing effect is still obtained, indicating that the mixed fluid anhydrous fiber dyeing technology of the present invention has good feasibility and can be used in natural A good water-free dyeing effect is obtained on cotton.
  • Table 5.1 and Table 5.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse yellow dye (omf is 2%).
  • 7.5g / L of saturated steam was introduced into the cage for pretreatment, and 15ml of acetone was added to the dye dissolution unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa supercritical CO 2 fluid, the fluid static dyeing is circulated for 1min after every 5min, the dyeing temperature is 130 °C, and the total dyeing time is 60min.
  • the float color cleaning temperature is 80 °C, the pressure is 20Mpa, the fluid static dyeing is circulated for 1min after every 5min, and the total cleaning time is 30min.
  • the related experimental results in Table 5.1 show that, using the anhydrous fiber dyeing method of the present invention, the reactive disperse yellow dye can achieve good dyeing effect on dry cotton fibers.
  • the hue angle h ° of the sample of Example 5 is 85.42, and the yellow shade is relatively pure, the chroma value C * is 22.34, and the color is more vivid.
  • the surface color depth value of the sample of Example 5 under the condition of a large fluid ratio of 1: 2000 It can also reach 0.921, which also proves that the sample of Example 5 after pretreatment has good dyeing and fixing properties.
  • Table 5.1 also shows that the standard deviation of the surface color depth value of the sample of Example 5 is also small. The value is 0.054, which indicates that the leveling property of the technology of the present invention on the sample of Example 5 is also very good.
  • Table 5.2 shows that using the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample of Example 5 is also better. Its fade level is 3-4. The color fastness to cotton, wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good.
  • Table 6.1 and Table 6.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse yellow dye (omf is 2%).
  • 10g / L of saturated steam was introduced into the yarn cage for pretreatment, and 15ml of acetone was added to the dye dissolution unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions were 20Mpa supercritical CO 2 fluid.
  • the fluid static dyeing cycled every 5 minutes for 1 minute, the dyeing temperature was 130 ° C, and the total dyeing time was 90 minutes.
  • the float color cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the fluid static dyeing is cycled every 5min for 1min
  • the total cleaning time is 30min.
  • Table 6.1 show that, using the anhydrous fiber dyeing method of the present invention, the reactive disperse yellow dye can achieve good dyeing effect on dry cotton fibers.
  • the hue angle h ° of the sample of Example 6 is 82.35, and its yellow shade is relatively pure.
  • the chroma value C * is 23.35, and the color is more vivid.
  • the sample of Example 6 is also under the condition of large fluid ratio, and its surface color depth value It can also reach 1.217, which also proves that the sample of Example 6 after pretreatment has good dyeing and fixing properties.
  • Table 6.1 also shows that the standard deviation of the color depth value of the sample surface of Example 6 is also small. The value is 0.035, indicating that the leveling property of the inventive technique on the sample of Example 6 is also very good.
  • Table 6.2 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample of Example 6 is also better. Its fading level is at level 4. The color fastness to cotton, wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good. The above results indicate that the present invention can also obtain a good anhydrous dyeing effect on the sample of Example 6.
  • Table 7.1 and Table 7.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse red dye (omf is 2%).
  • 7.5g / L of saturated steam was introduced into the cage for pretreatment, and 15ml of acetone was added to the dye dissolution unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions were 22Mpa supercritical CO 2 fluid, the fluid static dyeing was circulated for 1min every 5min, the dyeing temperature was 130 °C, and the total dyeing time was 60min.
  • the float color cleaning temperature is 80 °C, the pressure is 20Mpa, the fluid static dyeing is circulated for 1min every 5min, and the total cleaning time is 30min.
  • Table 7.1 show that, using the anhydrous fiber dyeing method of the present invention, the reactive disperse red dye can achieve good dyeing effect on dry cotton fibers.
  • the hue angle h ° of the sample of Example 7 is 2.01, and its yellow shade is relatively pure.
  • the chroma value C * is 23.89, and the color is more vivid.
  • the color depth of the surface of the sample of Example 7 is also under the condition of large fluid ratio It can also reach 1.275, which also proves that the sample of Example 7 after pretreatment has good dyeing and fixing properties.
  • Table 7.1 also shows that the standard deviation of the color depth value of the sample surface of Example 7 is also small. The value is 0.019, which indicates that the leveling property of the inventive technique on the sample of Example 7 is also very good.
  • Table 7.2 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample of Example 7 is also better. Its fading level is at level 4. The color fastness to cotton, wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good. The above results indicate that the present invention can also obtain a good anhydrous dyeing effect on the sample of Example 7.
  • Table 8.1 and Table 8.2 are the experimental results of using the method described in this example to dye pure cotton fibers with reactive disperse red dye (omf is 2%).
  • 10g / L of saturated steam was introduced into the yarn cage for pretreatment, and 15ml of acetone was added to the dye dissolution unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions were 20Mpa supercritical CO 2 fluid.
  • the float color cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the fluid static dyeing is circulated for 1min after every 5min
  • the total cleaning time is 30min.
  • the related experimental results in Table 8.1 show that, using the anhydrous fiber dyeing method of the present invention, the reactive disperse red dye can achieve good dyeing effect on dry cotton fibers.
  • the hue angle h ° of the sample of Example 8 is 1.27, the red color light is also more pure, the color is more vivid, and the C * value is increased to 25.98.
  • the sample of Example 8 is also under the same large proportion of fluid conditions, and its surface color depth value It can also reach 1.326, which also proves that the sample of Example 8 after pretreatment has good dyeing and fixing properties.
  • Table 8.1 also shows that the standard deviation of the color depth value of the sample surface of Example 8 is also small. The value is 0.087, indicating that the inventive technique is also excellent in level dyeing on the sample of Example 8.
  • Table 8.2 shows that using the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample of Example 8 is also better. Its fading level is at level 4. The color fastness to cotton, wool, acrylic, polyester, nylon and acetate can reach 4 or above, and the fastness to washing is good.
  • the anhydrous fiber dyeing method of the mixed fluid medium of the present invention uses a certain proportion of steam to mix into the fluid to increase the polarity of the CO 2 fluid and improve the hydrophilic fibers in the supercritical CO 2 fluid Dyeability and dyeing behavior. Not only can solve the problems of high energy consumption, high emissions, high pollution and other problems in the traditional water bath dyeing process, but also can obtain better dyeing results.
  • the present invention is convenient to operate, can effectively realize dry-state dyeing processing, and has a mild reaction, avoiding the use of a large amount of water, heat and high-concentration additives in the traditional dyeing process. Very broad.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coloring (AREA)

Abstract

本发明涉及一种混合流体介质的无水纤染方法，是将超临界二氧化碳流体介质与一定条件下的一定比例的蒸汽混合，从而形成一种混合流体介质，以提高及改善天然纤维的无水纤染效果。本发明技术通过混合流体介质的方法，可有效实现对疏水性超临界二氧化碳流体介质的改性，提高其极性，从而可在染色条件下增加极性染料的溶解度，并同时可起到膨化纤维的效果。因而，本发明技术显著地改善了亲水性纤维在超临界二氧化碳流体中的可染性及染色行为。且工艺简单、操作方便、能耗低，避免了传统工艺中大量水资源的消耗及污染物排放，具有绿色、生态、环保、高效的特点。

Description

一种混合流体介质的无水纤染方法 技术领域
本发明涉及纺织染整加工技术领域，尤其涉及一种混合流体介质的无水纤染方法。
背景技术
近年来，超临界流体技术已从单纯基础理论及实验室研究发展到实际应用领域。并在诸多领域中得到了快速提升和拓展，如超临界流体无水染色、超临界流体萃取、超临界流体化学反应、超临界流体清洗技术等。由于二氧化碳的临界温度和临界压力条件较为温和(31.1℃和7.38MPa)，且具有无毒、不燃、非爆性等特点，已成为当今应用最为广泛的超临界流体介质。超临界CO 2流体既有与气体相当的高渗透力和低粘度，又兼具有与液体相近的密度和对非极性物质优良的溶解能力。因此，它可以像液体那样溶解非极性或极性弱的染料，又可以像气体那样将溶解染料渗透于纤维之中，达到上染的目的。
超临界CO 2流体代替水作为染色介质，其基本理论基础是利用相似相容原理，将适用染料等以单分子状态溶解于流体介质中去，然后携带有染料的超临界CO 2流体向纤维表面发生传质，使染料分子发生吸附上染，并随流体进一步在纤维内部发生扩散和固着，从而到达染色目的。其中结构相对简单，分子质量小，极性较弱的染料易溶解于超临界CO 2流体中。因此，在以超临界二氧化碳流体为介质的染色加工中，一般分子较小且极性较弱的疏水性分散染料应用较多。同时，由于合成纤维如聚酯等同样具有疏水性特点，其在超临界二氧化碳流体中易于膨化，故合成纤维类可获得优良的染色效果。到目前为止，大部分合成纤维如聚酯等在超临界二氧化碳流体中的分散染料染色，可达到商业化标准。
但是，对于各类天然纤维，通常由于含有羟基、氨基等基团，其极性较大，在传统水浴染色过程中，一般都需要在水浴中先进行吸湿膨化，然后采用直接染料、活性染料、酸性染料等水溶性染料进行染色。然而，超临界CO 2流体介质的极性低，对极性高的水溶性染料不能实现良好溶解或几乎不容；而溶解于超临界CO 2流体的普通分散染料，由于其分子量小，分子结构简单，对天然纤维的亲和力或直接性低，不能获得良好的染色深度及色牢度等，故不能真正实现对各类天然纤维的良好染色。更为重要的是，疏水性二氧化碳流体无法对呈干态的天然纤维进行有效膨化，不能为染料分子的上染，特别是扩散提供必要条件。因此，解决天然纤维在超临界CO 2流体中的染色问题，具有十分重 要的意义。
发明内容
为解决上述技术问题，本发明的目的是为了克服现有技术存在的不足，提供一种以混合流体介质的无水纤染方法，其主要内容是：将超临界二氧化碳流体介质与一定条件下的一定比例的蒸汽混合，形成一种混合流体，并以此作为无水染色的加工介质。
本发明中，所述蒸汽用于改善超临界CO 2流体介质的极性，以增大染料在混合流体介质中的溶解度，同时蒸汽也起到了对干态天然纤维进行膨化，为染料的吸附上染提供必要条件的作用。
进一步的，其包括以下步骤：
(1)将呈干态的纤维采用机械压紧的方式，在特制多孔纱笼中以层状形式进行一定紧密度的踩“棉”或装填；
(2)将上述(1)中完成踩“棉”或装填的纱笼置于高压染缸中，密闭染缸后通入合适的非二氧化碳介质(即上述蒸汽)对干态纤维层进行一定压力和时间的预处理；
(3)在上述(2)中经预处理结束后，向高压染缸中通入超临界二氧化碳介质及溶解态专用染料，并按预定染色工艺进行增压、升温及保温染色；
(4)染色结束后，利用干净的超临界二氧化碳介质对染色系统同时进行一定条件下的在线浮色清洗和降温处理，然后对染色系统中流体介质进行回收至常压，并开盖出缸，完成超临界二氧化碳流体介质中的无水纤染加工。
进一步的，在步骤(1)中，所述的呈干态的纤维，可以为天然纤维中的短纤如棉花，或经加工后的麻类散纤，也可以为合成纤维如粘胶、涤纶、锦纶、腈纶类经加工成的短纤。
进一步的，所述步骤(1)中机械压紧方式为通过机械外力作用，对蓬松的纤维进行整齐、均匀的逐层挤压加工，使其能按照一定紧密度进行平整装填。通过逐层挤压加工，使得纤维的密实度更加均匀，有助于提高染色的均匀性。
进一步的，所述步骤(1)中，所述步骤(1)中，干态纤维以层状形式在纱笼中“踩棉”时，其一定紧密度为50-300kg/m 3。
进一步的，所述步骤(1)中特制多孔纱笼，为采用外覆特氟龙或由其他非导制热性表面材料制作而成，纱笼四周及其中心空管上分布有镂空的系列小孔。在染色的过程中，染缸内的温度往往超过了100℃，所述特氟龙或非导制热性表面材料能够减少传递 至纱笼内的纤维上的热量，避免对纤维造成损伤。
进一步的，所述步骤(2)中合适的非二氧化碳介质，可以为饱和蒸汽、过热蒸汽，其他极性溶剂中的一种或者几种。所述极性溶剂可为甲醇、乙醇、丙酮等。
进一步的，所述步骤(2)中一定压力和时间处理，其压力为0-1Mpa，时间为5～180min。
进一步的，在步骤(3)中，所述的溶解态专用染料为活性分散染料，其活性基为乙烯砜、乙烯基、均三嗪型、烟酸类结构中的一种或几种，或他们的衍生化合物。
进一步的，在步骤(3)中，所述溶解态专用染料，其溶解所用溶剂可以为超临界二氧化碳、乙醇、丙酮、甲醇、去离子水的一种或几种。
进一步的，在步骤(3)中，对于所用溶剂为两种混合溶剂时的比例，可以为1:5～5:1。
进一步的，在步骤(3)中，保温染色的过程中，通过循环泵使得混合流体在染色系统内循环流动，使得染料分子与纤维进行充分的接触。更优选的，流体在染色系统内呈动静循环的状态，即流体循环一定时间后，关闭循环泵，使得流体静置一定时间，再启动循环泵，重复上述操作，使得流体交替处于动静的状态。
进一步的，在步骤(3)中，所述的预定染色工艺中，温度为50-160℃，压力为7-35Mpa，流体的动静循环时间比为1:5-10:1，处理时间为10～180min。
进一步的，在步骤(4)中，所述的一定条件下的在线浮色清洗，其工艺为，温度为30-100℃，压力为8-35Mpa，流体的动静循环时间比为1:5-10:1，处理时间为10～120min。
进一步的，在步骤(4)中，染色完成后，通过循环系统将二氧化碳进行回收，以便下次循环利用，同时将染色系统内二氧化碳气体回收至大气压，以实现染缸的直接开盖。
本发明的技术方案具有如下显著特征及其优点：在本发明中，将超临界二氧化碳流体介质与一定条件下的一定比例的蒸汽混合，形成一种混合流体，并以此作为无水染色的加工介质。从而改善了超临界二氧化碳流体介质的极性，增大了染料在混合流体介质中的溶解度；同时，也实现了对干态天然纤维的有效膨化，为染料吸附上染提供了必要条件。因此，本发明技术可有效提高天然纤维的染色性能。并且其工艺简单，无需采用传统水浴，无染色废水产生，所需工艺流程短，效率高。染色结束后还可以采用流体对纤维进行在线清洗，除去浮色，从而得到品质良好的无水纤染干态产品。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并 可依照说明书的内容予以实施，以下以本发明的部分实施例并配合附图进行详细说明。
附图说明
图1是本发明实例提供的超临界二氧化碳流体中织物染色的系统原理图。
图1中：1、CO 2储罐；2,6,9,11,11’,13,14,15、截止阀；3、冷凝器；4、加压泵；5、预热器；7、染料溶解单元；8、过滤器；10、纤染染缸；12、循环泵；12’、气体回收泵；15、微调阀；16,19、温度计；17,20、压力表；18、分离釜；21、净化器。
图2为染缸的剖面图，其中：①、流体和染料入口；2、非CO 2介质入口截止阀；③、多孔纱笼；④、流体出口；⑤、快开结构；⑥、染缸密封盖；⑦、非CO 2介质出口；⑧、接口。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
本实验例所采用的短纤为纯棉纤维，染色前未经过处理的干态纤维；所用染料为超临界CO 2专用活性分散黄、活性分散红。
参见附图1、2所示，本发明实施例中所采用的一种混合流体介质的无水纤染方法步骤为如下。将呈干态的纤维采用机械压紧的方式，在特制多孔纱笼以层状形式进行一定紧密度装填(参看图2中多孔纱笼图)，然后将纱笼密闭，关闭染缸密封盖⑥。关闭系统中截止阀9、14，打开非CO 2介质入口截止阀②，向染缸内通入一定量的饱和蒸汽。然后关闭截止阀②、11、11’，打开截止阀9，向染缸10(图1)内通入溶解染料和CO 2流体。并根据预定的染色工艺流程及参数，启动由CO 2储罐1、冷凝器3、加压泵4、预热器5在内的加压系统对染色循环系统增压和流体预热和升温，使之有效形成一种混合流体介质，并使染料溶解单元7内的染料充分溶解。当染色循环系统温度达到预定温度如120℃、压力达到预设值如20Mpa后，加压泵4停泵，并关闭截止阀6，开启染色循环回路中循环泵12。使溶解染料随形成的混合流体循环，并与待染纤维充分上染。染料上染过程中混合流体循环时间与静态时间比为5:1。在静态及循环条件下溶解染料通过自身的分子热运动及流体传质与多孔纱笼③中纤维充分接触，并完成吸附上染、扩散 及固着过程。
保温保压染色完成后，开启微调阀15对系统泄压，利用由气体回收泵12’、分离釜18、净化器21、冷凝器3等组成的分离回收系统对染色循环系统中的染料及混合流体进行分离和回收。
混合流体分离回收结束后，再次重复上述操作对纤维进行二氧化碳流体在线清洗，温度为30-100℃，压力为8-35Mpa、二氧化碳流体的动静循环时间比为1:5-10:1，清洗时间为10～120min。清洗结束后，再利用泄压系统对气体、染料进行分离回收，并使染缸中压力达到大气压。最后开启纤染染缸10，将染色纤维从纱笼装置里取出。参照上述处理步骤及工艺，经本次试验方案，用活性分散染料对棉纤维进行染色，其分析测试及其结果如下。
1.无水纤染样品颜色特征值的测定及匀染性评价
利用Hunterlab Ultrascan PRO型分光测色仪对混合流体介质中无水纤染样品进行表面色深值(K/S)及色度值(L*、a*、b*、C*和h°)的测定。测试时，选择D 65光源，10°视角，纤维均匀混合制样，每个样品随机测试8个点，最后计算算术平均值。
纤维的匀染性由被测样品在最大吸收波长处表面色深值的标准差
Figure PCTCN2018111893-appb-000001
来衡量，计算方式如(1)所示。
Figure PCTCN2018111893-appb-000002
其中，i代表第i个测试点(i＝1,2,3,…..,n；此处n＝8)；
Figure PCTCN2018111893-appb-000003
代表第i个测试点在最大吸收波长处的表面色深值；
Figure PCTCN2018111893-appb-000004
代表n个测试点在最大吸收处表面色深值的算术平均值，计算方式如(2)所示。
2.色牢度性能测试
依照GB/T 3921-2008对混合流体介质中无水纤染样品进行耐皂洗色牢度的评定，即将适量样品与多组分贴衬(SDC Multifiber DW,SDC enterprises CO.，Ltd.，UK)样缝合，作为组合试样，皂液浓度为5g/L，浴比为1:50，耐洗色牢度试验机的工作温度为 40℃，洗涤30min。洗涤结束后取出组合试样，用清水冲洗，并在室温下自然晾干。然后在D 65光源下，利用褪色样卡和沾色样卡分别对试样的变色和贴衬的沾色情况进行评级。
实施例1
表1.1和表1.2是采用本实施例所述方法，对纯棉纤维采用活性分散黄染料(o.m.f为5％)进行染色加工的实验结果。染色时系统内混合流体中蒸汽的含量为2.5g/L，并在染料溶解单元中加入10ml丙酮对染料进行预溶解。染色上染条件为20Mpa的混合流体介质，混合流体静态染色每5min后循环1min，染色温度120℃，总的上染时间为60min。染色结束后，超临界CO 2流体浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表1.1 实施例1样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000005
表1.2 实施例1样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000006
表1.1中相关实验结果显示，以活性分散黄为染料，采用本发明的混合流体无水纤染方法，对干态棉纤维可获得良好的染色效果。实施例1的无水纤染样品的色相角h°为88.30，其黄色色光较为纯正，颜色也较为鲜艳。同时，在1:2000的大流体比条件下，其表面色深值
Figure PCTCN2018111893-appb-000007
可达到1.124，显示出其在本发明技术条件下具有良好的上染、固着性能。同时，表1.1还表明，实施例1样品表面色深值的标准差较小，其
Figure PCTCN2018111893-appb-000008
值为0.045，表明实施例1样品匀染性优良。
表1.2显示，实施例1样品的常规色牢度较好，其褪色级数在3-4级。在腈纶、涤 纶和醋酯上的沾色牢度都可达到4级或以上。而对于棉、羊毛，尼龙的沾色牢度也在3-4级。
实施例2
表2.1和表2.2是采用本实施例所述方法，对纯棉纤维采用活性分散黄染料(o.m.f为5％)进行染色加工的实验结果。染色时系统内混合流体中蒸汽的含量为2.5g/L，并在染料溶解单元中加入10ml甲醇对染料进行预溶解。染色上染条件为20Mpa的混合流体介质，混合流体静态染色每5min后循环1min，染色温度120℃，总的上染时间为60min。染色结束后，超临界CO 2流体浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表2.1 实施例2样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000009
表2.2 实施例2样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000010
表2.1中相关实验结果显示，以活性分散黄为染料，采用本发明的混合流体无水纤染方法，对干态棉纤维可获得良好的染色效果。实施例2样品的色相角h°为84.97，其黄色色光也较为纯正，颜色更为鲜艳，C*值增大为23.23。同时，实施例2样品也在相同大比例流体条件下，其表面色深值
Figure PCTCN2018111893-appb-000011
也可达到1.280，同样证明了实施例2样品有良好的上染和固着性能。同时，表2.1还表明，实施例2样品表面色深值的标准差也较小，其
Figure PCTCN2018111893-appb-000012
值为0.022，表明本发明技术在实施例2样品上的匀染性也非常优良。
表2.2显示，实施例2样品的常规色牢度也较好，其褪色级数在3-4级。在棉、羊 毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。
实施例3
表3.1和表3.2是采用本实施例所述方法，对纯棉纤维采用活性分散黄染料(o.m.f为2％)进行染色加工的实验结果。染色时系统内混合流体中蒸汽的含量为5g/L，并加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa的混合流体，混合流体静态染色每5min后循环1min，染色温度130℃，总的上染时间为40min。染色结束后，超临界CO 2流体浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表3.1 实施例3样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000013
表3.2 实施例3样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000014
表3.1中实验结果显示，以活性分散黄为染料，采用本发明的混合流体无水纤染方法，对干态棉纤维可获得良好的染色效果。获得的样品的色相角h°为87.02，其黄色色光也较为纯正。其C*值为23.04，颜色较为鲜艳。同时，实施例3也在相同大比例流体条件下进行，其样品的表面色深值
Figure PCTCN2018111893-appb-000015
也可达到0.949，同样证明了实施例3条件下，专用染料在干态棉纤维上具有良好的上染和固着性能。而且，表3.1还表明，在本实验条件下样品表面色深值的标准差也较小，其
Figure PCTCN2018111893-appb-000016
值为0.020，表明实施例3中的混合流体无水纤染样品匀染性也非常优良。
表3.2显示，实施例3中的样品常规色牢度也较好，其褪色牢度达到4级。在棉、羊毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。
实施例4
表4.1和表4.2是采用本实施例所述方法，对纯棉纤维采用活性分散红染料(o.m.f为2％)进行染色加工的实验结果。染色时系统内混合流体中蒸汽的含量为5g/L，并加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa的混合流体，混合流体静态染色每5min后循环1min，染色温度130℃，总的上染时间为40min。染色结束后，超临界CO 2流体浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表4.1 实施例4样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000017
表4.2 实施例4样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000018
表4.1中的相关实验结果显示，采用本发明的混合流体无水纤染方法，活性分散红染料染色在干态棉纤维可获得良好的染色效果。其样品的色相角h°为4.36，色度指数b*值较小，其红色色光较为纯正。其C*值为15.01，其颜色较为鲜艳。同时，在实施例4的大比例流体条件下，其表面色深值
Figure PCTCN2018111893-appb-000019
也可达到0.954，同样证明了在实施例4的混合流体无水纤染条件下，专用染料在干态棉纤维上具有良好的上染和固着性能。此外，表4.1还表明，该样品的表面色深值标准差也较小，其
Figure PCTCN2018111893-appb-000020
值为0.051，表明实施例4中混合流体无水纤染样品的匀染性也非常优良。
表4.2显示，采用本发明的混合流体无水纤染方法，其样品的常规色牢度也较优良。其褪色牢度可达4级。在棉、羊毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。因而，上述结果表明，在选用活性分散红染色干态棉纤维的条件下，依然获得了良好的无水染色效果，说明本发明的混合流体无水纤染技术具有良 好的可行性，能在天然棉上获得良好的无水染色效果。
实施例5
表5.1和表5.2是采用本实施例所述方法，对纯棉纤维采用活性分散黄染料(o.m.f为2％)进行染色加工的实验结果。染色前通入7.5g/L的饱和蒸汽在纱笼中进行预处理，并在染料溶解单元中加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界CO 2流体，流体静态染色每5min后循环1min，染色温度130℃，总的上染时间为60min。染色结束后，浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表5.1 实施例5样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000021
表5.2 实施例5样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000022
表5.1中相关实验结果显示，采用本发明的无水纤染方法，活性分散黄染料染色在干态棉纤维可获得良好的染色效果。实施例5样品的色相角h°为85.42，其黄色色光也较为纯正，彩度值C*的值为22.34，颜色较为鲜艳。同时，实施例5样品在1：2000的大流体比条件下，其表面色深值
Figure PCTCN2018111893-appb-000023
也可达到0.921，同样证明了经过预处理后的实施例5样品有良好的上染和固着性能。同时，表5.1还表明，实施例5样品表面色深值的标准差也较小，其
Figure PCTCN2018111893-appb-000024
值为0.054，表明本发明技术在实施例5样品上的匀染性也非常优良。
表5.2显示，采用本发明的无水纤染方法，实施例5样品的常规色牢度也较好。其褪色级数在3-4级。在棉、羊毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。
实施例6
表6.1和表6.2是采用本实施例所述方法，对纯棉纤维采用活性分散黄染料(o.m.f为2％)进行染色加工的实验结果。染色前通入10g/L的饱和蒸汽在纱笼中进行预处理，并在染料溶解单元中加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界CO 2流体，流体静态染色每5min后循环1min，染色温度130℃，总的上染时间为90min。染色结束后，浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表6.1 实施例6样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000025
表6.2 实施例6样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000026
表6.1中相关实验结果显示，采用本发明的无水纤染方法，活性分散黄染料染色在干态棉纤维可获得良好的染色效果。实施例6样品的色相角h°为82.35，其黄色色光也较为纯正，彩度值C*的值为23.35，颜色较为鲜艳。同时，实施例6样品同样在大流体比条件下，其表面色深值
Figure PCTCN2018111893-appb-000027
也可达到1.217，同样证明了经过预处理后的实施例6样品有良好的上染和固着性能。同时，表6.1还表明，实施例6样品表面色深值的标准差也较小，其
Figure PCTCN2018111893-appb-000028
值为0.035，表明本发明技术在实施例6样品上的匀染性也非常优良。
表6.2显示，采用本发明的无水纤染方法，实施例6样品的常规色牢度也较好。其褪色级数在4级。在棉、羊毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。上述结果表明，本发明也能在实施例6样品上获得良好的无水染色效果。
实施例7
表7.1和表7.2是采用本实施例所述方法，对纯棉纤维采用活性分散红染料(o.m.f为2％)进行染色加工的实验结果。染色前通入7.5g/L的饱和蒸汽在纱笼中进行预处理，并在染料溶解单元中加入15ml丙酮对染料进行预溶解。染色上染条件为22Mpa超临界CO 2流体，流体静态染色每5min后循环1min，染色温度130℃，总的上染时间为60min。染色结束后，浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表7.1 实施例7样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000029
表7.2 实施例7样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000030
表7.1中相关实验结果显示，采用本发明的无水纤染方法，活性分散红染料染色在干态棉纤维可获得良好的染色效果。实施例7样品的色相角h°为2.01，其黄色色光也较为纯正，彩度值C*的值为23.89，颜色较为鲜艳。同时，实施例7样品同样在大流体比条件下，其表面色深值
Figure PCTCN2018111893-appb-000031
也可达到1.275，同样证明了经过预处理后的实施例7样品有良好的上染和固着性能。同时，表7.1还表明，实施例7样品表面色深值的标准差也较小，其
Figure PCTCN2018111893-appb-000032
值为0.019，表明本发明技术在实施例7样品上的匀染性也非常优良。
表7.2显示，采用本发明的无水纤染方法，实施例7样品的常规色牢度也较好。其褪色级数在4级。在棉、羊毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。上述结果表明，本发明也能在实施例7样品上获得良好的无水染色效果。
实施例8
表8.1和表8.2是采用本实施例所述方法，对纯棉纤维采用活性分散红染料(o.m.f为2％)进行染色加工的实验结果。染色前通入10g/L的饱和蒸汽在纱笼中进行预处理，并在染料溶解单元中加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界CO 2流体，流体静态染色每5min后循环1min，染色温度130℃，总的上染时间为90min。染色结束后，浮色清洗温度为80℃，压力为20Mpa，流体静态染色每5min后循环1min，总清洗时间为30min。
表8.1 实施例8样品颜色特征值的测定及匀染性评价
Figure PCTCN2018111893-appb-000033
表8.2 实施例8样品的耐水洗牢度评价
Figure PCTCN2018111893-appb-000034
表8.1中相关实验结果显示，采用本发明的无水纤染方法，活性分散红染料染色在干态棉纤维可获得良好的染色效果。实施例8样品的色相角h°为1.27，其红色色光也较为纯正，颜色更为鲜艳，C*值增大为25.98。同时，实施例8样品也在相同大比例流体条件下，其表面色深值
Figure PCTCN2018111893-appb-000035
也可达到1.326，同样证明了经过预处理后的实施例8样品有良好的上染和固着性能。同时，表8.1还表明，实施例8样品表面色深值的标准差也较小，其
Figure PCTCN2018111893-appb-000036
值为0.087，表明本发明技术在实施例8样品上的匀染性也非常优良。
表8.2显示，采用本发明的无水纤染方法，实施例8样品的常规色牢度也较好。其褪色级数在4级。在棉、羊毛、腈纶、涤纶、尼龙和醋酯的沾色牢度都可达到4级或以上，耐水洗牢度良好。
由上述实施例可知，本发明的混合流体介质的无水纤染方法，利用一定比例的蒸汽 混入流体中，以提高CO 2流体的极性，改善了亲水性纤维在超临界CO 2流体中可染性及染色行为。不但可以解决传统水浴染色过程中高能耗、高排放、高污染等问题，且能获得较好的染色效果。同时，本发明操作方便，可有效实现干态染色加工，且反应温和，避免了传统染色工艺中大量水、热和高浓度助剂的使用，具有高效、绿色、环保等特点，因此其应用前景非常广阔。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (15)

  1. 一种混合流体介质的无水纤染方法，其特征主要在于：
    将超临界二氧化碳流体介质与一定条件下的一定比例的蒸汽混合，形成一种混合流体，并以此作为无水染色的加工介质。
  2. 根据权利要求1所述的一种混合流体介质的无水纤染方法，其步骤主要在于：
    (1)将呈干态的纤维采用机械压紧的方式，在特制多孔纱笼中以层状形式进行一定紧密度的踩“棉”或装填；
    (2)将上述(1)中完成踩“棉”或装填的多孔纱笼置于高压染缸中，密闭染缸后通入合适的非二氧化碳介质对干态纤维层进行一定压力和时间的预处理；
    (3)上述(2)中预处理结束后，向高压染缸中通入超临界二氧化碳介质及溶解态专用染料，并按预定染色工艺进行增压、升温及保温染色；
    (4)染色结束后，利用干净的超临界二氧化碳介质对染色系统同时进行一定条件下的在线浮色清洗和降温处理，然后对染色系统中流体介质进行回收至常压，并开盖出缸，完成超临界二氧化碳流体介质中的无水纤染加工。
  3. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述呈干态的纤维，为天然纤维中的短纤如棉花，或经加工后的麻类散纤，或合成纤维如粘胶、涤纶、锦纶、腈纶类经加工成的短纤。
  4. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述步骤(1)中机械压紧方式为通过机械外力作用，对蓬松的纤维进行整齐、均匀的逐层挤压加工，使其能按照一定紧密度进行平整装填。
  5. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述步骤(1)中的特制多孔纱笼，为采用外覆特氟龙或其他非导制热性表面材料制作而成，纱笼四周及其中心空管上分布有镂空的系列小孔。
  6. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述步骤(1)，所述层状形式是指经机械“踩棉”或填装时，干态纤维以一定厚度的平整挤压填装作为一层，然后再进行下一层的挤压填装，并反复逐层进行，在特制纱笼中完成预定加工量的“踩棉”。
  7. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述步骤(1)中，干态纤维以层状形式在多孔纱笼中“踩棉”时，其一定紧密度为50-300kg/m 3。
  8. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述步骤(2)中合适的非二氧化碳介质，为饱和蒸汽、过热蒸汽，其他极性溶剂中的一种或者几种。
  9. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：所述步骤(2)中一定压力和时间的预处理，其压力为0-1Mpa，时间为5～180min。
  10. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：在步骤(3)中，所述的溶解态专用染料为活性分散染料，其活性基为乙烯砜、乙烯基、均三嗪型、烟酸类结构中的一种或几种，或他们的衍生化合物。
  11. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：在步骤(3)中，所述溶解态专用染料，其溶解所用的溶剂为超临界二氧化碳、乙醇、丙酮、甲醇、去离子水的一种或几种。
  12. 根据权利要求11所述的一种混合流体介质的无水纤染方法，其特征在于：在步骤(3)中，对于所用溶剂为两种混合溶剂时的比例，为1:5～5:1。
  13. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：在步骤(3)中，所述的预定染色工艺中，温度为50-160℃，压力为7-35Mpa，流体的动静循环时间比为1:5-10:1，处理时间为10～180min。
  14. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：在步骤(4)中，所述的在线浮色清洗，其工艺为，温度为30-100℃，压力为8-35Mpa，流体的动静循环时间比为1:5-10:1，处理时间为10～120min。
  15. 根据权利要求2所述的一种混合流体介质的无水纤染方法，其特征在于：在步骤(4)中，染色完成后，通过循环系统将二氧化碳进行回收，以便下次循环利用，同时将染色系统内二氧化碳气体回收至大气压，以实现染缸的直接开盖。
PCT/CN2018/111893 2018-10-16 2018-10-25 一种混合流体介质的无水纤染方法 WO2020077665A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/346,227 US11560669B2 (en) 2018-10-16 2018-10-25 Fiber dyeing method using mixed fluid medium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811202689.0 2018-10-16
CN201811202689.0A CN109355928B (zh) 2018-10-16 2018-10-16 一种混合流体介质的无水纤染方法

Publications (1)

Publication Number Publication Date
WO2020077665A1 true WO2020077665A1 (zh) 2020-04-23

Family

ID=65349160

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/111893 WO2020077665A1 (zh) 2018-10-16 2018-10-25 一种混合流体介质的无水纤染方法

Country Status (3)

Country Link
US (1) US11560669B2 (zh)
CN (1) CN109355928B (zh)
WO (1) WO2020077665A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112111887A (zh) * 2020-05-27 2020-12-22 山东出彩无水纤染高科有限公司 天然纤维及其制品的一种超临界混合流体闪爆处理方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111535017B (zh) * 2020-05-27 2022-04-15 苏州大学 一种用于天然纤维超临界co2流体闪爆处理的方法
CN111576060B (zh) * 2020-05-27 2023-11-17 山东出彩无水纤染高科有限公司 天然纤维及其制品的一种超临界co2流体闪爆处理方法
WO2021237514A1 (zh) * 2020-05-27 2021-12-02 南通纺织丝绸产业技术研究院 一种超临界二氧化碳流体闪爆机
WO2022095053A1 (zh) * 2020-11-07 2022-05-12 山东高棉智能纤染科技有限公司 天然纤维及其制品的一种超临界混合流体闪爆处理方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001226884A (ja) * 1999-12-06 2001-08-21 Howa Kk 超臨界染液による染色方法
CN1310257A (zh) * 2000-02-16 2001-08-29 斯刀克布拉邦特股份有限公司 在超临界流体中对纺织材料染色的方法
JP2002201575A (ja) * 2000-12-27 2002-07-19 Okayama Prefecture セルロース系繊維の染色方法
JP2006016711A (ja) * 2004-06-30 2006-01-19 Teijin Techno Products Ltd ポリエステル繊維の染色方法
CN102296469A (zh) * 2011-07-07 2011-12-28 苏州大学 在超临界二氧化碳流体中天然纤维的染色方法
CN104420096A (zh) * 2013-08-26 2015-03-18 香港生产力促进局 一种超临界流体的纺织材料无水整理方法
CN104562759A (zh) * 2013-10-29 2015-04-29 李长娟 散纤维染色工艺
CN105133396A (zh) * 2015-08-26 2015-12-09 青岛国邦工业科技发展有限公司 一种超临界co2印染工艺
CN106835758A (zh) * 2016-11-21 2017-06-13 大连工业大学 一种麻类粗纱超临界二氧化碳生物酶煮漂染方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015032022A1 (zh) * 2013-09-03 2015-03-12 苏州大学 一种对纺织品进行固色加工的方法及其装置
CN104594072A (zh) * 2015-02-02 2015-05-06 广东溢达纺织有限公司 一种活性染料的非水介质染色方法
MX2017014106A (es) * 2015-05-08 2018-07-06 Thies Gmbh & Co Kg Procedimiento de tratamiento de un sustrato textil, asi como dispositivos para la realizacion del procedimiento.
CN105713419A (zh) * 2016-01-21 2016-06-29 苏州印丝特纺织数码科技有限公司 一种高纯度芡实壳天然染料的制备方法及其染色方法
CN107558041A (zh) * 2017-09-22 2018-01-09 江苏欣捷衬布有限公司 一种坯布的染整工艺
CN108411538B (zh) * 2018-04-20 2020-07-14 江苏汇鸿国际集团中锦控股有限公司 一种常温常压条件下成衣染色和成衣水洗的工艺

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001226884A (ja) * 1999-12-06 2001-08-21 Howa Kk 超臨界染液による染色方法
CN1310257A (zh) * 2000-02-16 2001-08-29 斯刀克布拉邦特股份有限公司 在超临界流体中对纺织材料染色的方法
JP2002201575A (ja) * 2000-12-27 2002-07-19 Okayama Prefecture セルロース系繊維の染色方法
JP2006016711A (ja) * 2004-06-30 2006-01-19 Teijin Techno Products Ltd ポリエステル繊維の染色方法
CN102296469A (zh) * 2011-07-07 2011-12-28 苏州大学 在超临界二氧化碳流体中天然纤维的染色方法
CN104420096A (zh) * 2013-08-26 2015-03-18 香港生产力促进局 一种超临界流体的纺织材料无水整理方法
CN104562759A (zh) * 2013-10-29 2015-04-29 李长娟 散纤维染色工艺
CN105133396A (zh) * 2015-08-26 2015-12-09 青岛国邦工业科技发展有限公司 一种超临界co2印染工艺
CN106835758A (zh) * 2016-11-21 2017-06-13 大连工业大学 一种麻类粗纱超临界二氧化碳生物酶煮漂染方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112111887A (zh) * 2020-05-27 2020-12-22 山东出彩无水纤染高科有限公司 天然纤维及其制品的一种超临界混合流体闪爆处理方法
CN112111887B (zh) * 2020-05-27 2023-10-27 山东出彩无水纤染高科有限公司 天然纤维及其制品的一种超临界混合流体闪爆处理方法

Also Published As

Publication number Publication date
US20210324577A1 (en) 2021-10-21
CN109355928B (zh) 2022-01-18
CN109355928A (zh) 2019-02-19
US11560669B2 (en) 2023-01-24

Similar Documents

Publication Publication Date Title
WO2020077665A1 (zh) 一种混合流体介质的无水纤染方法
WO2020077702A1 (zh) 一种以超临界二氧化碳流体为介质的无水纤染方法
WO2020077701A1 (zh) 棉花的一种无水纤染方法
US10801146B2 (en) System for anhydrous boiling, bleaching and dyeing using supercritical carbon dioxide fluid
CN102787459B (zh) 一种超临界二氧化碳筒子纱染色釜及其无水染色方法
CN107419462B (zh) 一种超临界二氧化碳染色系统及染色工艺
WO2020077666A1 (zh) 一种适用于混合流体介质的无水纤染染色机
CN101368343B (zh) 一种超临界co2介导的拼色染色方法
CN106637753A (zh) 一种染色釜、芳纶纤维超临界二氧化碳无水染色装置及染色方法
CN108086022B (zh) 纺织品用超临界co2流体染料组合物及染色系统和方法
CN102392367B (zh) 在低压二氧化碳介质中活性分散染料的固色方法
CN107904986B (zh) 超临界co2流体天然纺织染料组合物及染色方法
CN101125433B (zh) 采用增压与减压工艺的木材染色法
Rippon for Wool Dyeing1
CN106468026A (zh) 用于超临界co2流体染色的棉纤维染料及其染色方法
CN111472182A (zh) 一种高温高压少水染色工艺
CN203228293U (zh) 竹材碳化染色连续加工装备
CN111576060B (zh) 天然纤维及其制品的一种超临界co2流体闪爆处理方法
CN103710926B (zh) 一种用于超细纤维合成革染色的废水循环染色机
CN113005790B (zh) 助染剂及其在偶联型分散染料仿麂皮织物染色中的应用
CN112111887B (zh) 天然纤维及其制品的一种超临界混合流体闪爆处理方法
Abou Elmaaty et al. Development of textile dyeing using the green supercritical fluid technology: A Review
WO2021237514A1 (zh) 一种超临界二氧化碳流体闪爆机
WO2022095053A1 (zh) 天然纤维及其制品的一种超临界混合流体闪爆处理方法
WO2021237519A1 (zh) 一种用于天然纤维超临界co2流体闪爆处理的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18937441

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18937441

Country of ref document: EP

Kind code of ref document: A1