WO2020077702A1 - 一种以超临界二氧化碳流体为介质的无水纤染方法 - Google Patents

一种以超临界二氧化碳流体为介质的无水纤染方法 Download PDF

Info

Publication number
WO2020077702A1
WO2020077702A1 PCT/CN2018/114040 CN2018114040W WO2020077702A1 WO 2020077702 A1 WO2020077702 A1 WO 2020077702A1 CN 2018114040 W CN2018114040 W CN 2018114040W WO 2020077702 A1 WO2020077702 A1 WO 2020077702A1
Authority
WO
WIPO (PCT)
Prior art keywords
dyeing
carbon dioxide
supercritical carbon
fluid
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/114040
Other languages
English (en)
French (fr)
Inventor
龙家杰
蔡冲
高潮
高威
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Gaomei Group Co Ltd
Suzhou University
Original Assignee
Shandong Gaomei Group Co Ltd
Suzhou University
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 Shandong Gaomei Group Co Ltd, Suzhou University filed Critical Shandong Gaomei Group Co Ltd
Priority to US16/346,244 priority Critical patent/US11608592B2/en
Publication of WO2020077702A1 publication Critical patent/WO2020077702A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • D06P1/94—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
    • 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
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D06M13/53—Cooling; Steaming or heating, e.g. in fluidised beds; with molten metals
    • 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
    • D06P7/00—Dyeing or printing processes combined with mechanical treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • 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
    • D06P3/66—Natural or regenerated cellulose using reactive dyes

Definitions

  • the invention relates to an anhydrous fiber dyeing method using supercritical carbon dioxide fluid as a medium, and belongs to the technical field of textile dyeing and finishing.
  • Supercritical CO 2 fluid (Supercritical Carbon Dioxide Fluid, SCF-CO 2 ) replaces water as a dyeing medium, and has a short process flow, easy operation, and no industrial wastewater pollution, completely solving the environment caused by textile processing Problems caused by pollution.
  • Supercritical CO 2 has the property of partial gas, with low viscosity, high diffusion coefficient, and small diffusion boundary, which shortens the dyeing time.
  • the fluid can be released in a gaseous form to achieve the recovery of residual solid dyes and gases, no drying treatment after dyeing is required, and little or no dye additives can be added to achieve resources Optimal use of the protection of the ecological environment.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and to provide a method of water-free fiber dyeing using supercritical carbon dioxide fluid as a medium.
  • the first object of the present invention is to provide an anhydrous fiber dyeing method using supercritical carbon dioxide fluid as a medium, characterized in that it includes the following steps:
  • the dry fiber is mechanically compacted in a special porous yarn cage in a layered form with a certain degree of dry stepping on "cotton" or filling;
  • the dry fiber is short fiber of natural fiber such as cotton, or processed hemp loose fiber, or synthetic fiber such as viscose, polyester, nylon, acrylic fiber processed staple fiber.
  • the mechanical compaction method is to perform a uniform and uniform layer-by-layer extrusion process on the fluffy cotton by the action of mechanical external force, so that it can be smoothly packed according to a certain tightness.
  • the specially-made porous yarn cage is made by covering Teflon or other non-conductive thermal surface materials, and there are several hollow holes distributed around the yarn cage and on the central hollow tube.
  • the layered form refers to mechanically "stepping on cotton” or dry fiber extrusion filling during filling as a layer, and then performing the next layer of extrusion filling, And repeated layer by layer, in a special yarn cage to complete the predetermined processing amount of "stepping cotton".
  • step (1) when the dry fiber is "stepped on cotton" in the yarn cage in a layered form, its certain tightness is 50-300 kg / m 3 .
  • the pretreatment medium in step (2) may be one or more of saturated steam, superheated steam, or other polar solvents.
  • the main condition of the pretreatment in the step (2) is pressure 0-1Mpa, time 5 ⁇ 180min.
  • the dissolved special dye is a reactive disperse dye, and its reactive group is one or more of vinyl sulfone, vinyl, mesitazine type, nicotinic acid structure, or they Derived compounds.
  • the solvent for dissolving the dedicated dye is 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.
  • 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 temperature of the system is reduced to a certain temperature, and its temperature is 30-100 ° C.
  • step (4) the online float color cleaning under certain conditions, the process conditions are: temperature is 30-100 °C, pressure is 8-35Mpa, fluid dynamic and static cycle time ratio is 1: 5 -10: 1, the processing time is 10 ⁇ 120min.
  • step (4) after the dyeing is completed, the carbon dioxide is separated and recovered by the recovery 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 is as follows:
  • dry fibers are packed in a layered form in a special porous yarn cage by mechanical compaction in a layered form, so that the fibers have a compact structure in the device, are evenly distributed, and pass a certain medium
  • 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.
  • the present invention has at least the following advantages:
  • the present invention can not only solve the problems of high energy consumption, high emissions, high pollution and the like in the traditional water bath dyeing process, but also obtain good dyeing effects.
  • the process of the invention is simple, the operation is convenient, and the dry dyeing process can be effectively realized. And the reaction is mild, avoiding the use of a large amount of water, heat and high concentration of additives in the traditional dyeing process, with high efficiency, green, environmental protection and other characteristics.
  • FIG. 1 is a schematic diagram of a system for dyeing fabric in supercritical carbon dioxide fluid provided by the present invention
  • Figure 2 is a cross-sectional view of a fiber dyeing and dyeing cylinder, in which: 1, fluid and dye inlet; 2, non-carbon dioxide medium inlet shut-off valve; 3, (porous) yarn cage; 4, fluid outlet; Cover; 7, non-carbon dioxide medium inlet; 8, interface.
  • the staple fibers used in the embodiments of the present invention are pure cotton fibers, which are 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 supercritical carbon dioxide fluid anhydrous fiber dyeing used in the embodiments of the present invention are as follows: the fibers in a dry state are mechanically compressed in a layered form in a special porous yarn cage Carry out a certain degree of tightness filling (refer to the picture of the yarn cage in Figure 2), then close the yarn cage and close the sealing cover of the dyeing tank 6.
  • shut-off valves 9, 14 in the system open the non-CO 2 medium inlet shut-off valve 2, pass a certain amount of non-carbon dioxide medium (such as saturated steam, etc.) into the dyeing tank, and adjust the opening and closing degree of the shut-off valve 11 'in the system to maintain
  • the certain pressure in the dyeing tank is 0-1.0Mpa, and the fiber is pretreated for 5 ⁇ 180min.
  • 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, And the dye in the dye dissolving unit 7 is fully dissolved.
  • a predetermined temperature such as 120 ° C.
  • 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 fluid and fully dyed with the fiber to be dyed.
  • the ratio of fluid circulation time to fluid static time during dye uptake is 5: 1. Under static and circulating conditions, the dissolved dye fully contacts the fibers in the (porous) sarong 3 through its own molecular thermal motion and fluid mass transfer, and completes the adsorption, dyeing, diffusion, and fixation processes.
  • the fine-tuning valve 15 is opened to relieve the pressure of the system, and the dye and fluid in the dyeing circulation system are separated by the separation and recovery system composed of a gas recovery pump 12 ', a separation kettle 18, a purifier 21, a condenser 3 Separation and recycling.
  • the temperature is 30-100 °C
  • the pressure is 8-35Mpa
  • the dynamic and static circulation time ratio of the fluid is 1: 5-10: 1
  • the cleaning time is 10 ⁇ 120min .
  • use the pressure relief system to separate and recover the gas and dye, and make the pressure in the dyeing tank reach atmospheric pressure.
  • the fiber dyeing cylinder 10 is opened, and the dyed fibers are taken out of the yarn cage device.
  • the surface color depth value (K / S) and chromaticity value (L *, a *, b *, C *, and h °) of the water-fiber dyed samples in supercritical CO2 fluid were measured using Hunterlab Ultrascan PRO spectrophotometer Of determination. During the test, choose D65 light source, 10 ° viewing angle, the fibers are mixed uniformly for sample preparation, each sample is randomly tested for 8 points, and finally the arithmetic average is calculated.
  • 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).
  • the supercritical CO 2 anhydrous fiber dyed samples were evaluated for soaping color fastness, that is, an appropriate amount of samples and multi-component paste (SDC Multifiber DW, SDC enterprises CO., Ltd., UK )
  • Sample suture as a combined sample, the soap concentration is 5g / L, the bath ratio is 1:50, the working temperature of the color fastness tester is 40 ° C, and the washing is for 30 minutes. After washing, the combined sample is taken out, rinsed with clean water, and air-dried at room temperature. Then under the D 65 light source, use the fading sample card and staining sample card to evaluate the discoloration of the sample and the staining of the liner respectively.
  • Table 1 and Table 2 are the experimental results of using the method described in this example to dye 1 g of pure cotton fiber with disperse reactive yellow dye (o.m.f is 5%).
  • 2.5g / L of saturated steam was introduced into the cage for pretreatment, and 10ml of acetone was added to the dye dissolution unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa supercritical carbon dioxide fluid.
  • the fluid static dyeing cycle is every 1min after 1min, the dyeing temperature is 120 °C, the bath ratio is 1: 2000, and the total dyeing time is 60min.
  • the online cleaning temperature is 80 °C, the pressure is 20Mpa, and the total cleaning time is 30min.
  • Table 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 Example 1 anhydrous fiber dyed sample was 88.30, the yellow shade was more pure and the color was more vivid.
  • Table 1 shows that the standard deviation of the color depth value of the sample surface of Example 1 is small, and its The value is 0.045, indicating that the sample of Example 1 has excellent levelness.
  • Table 2 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample of Example 1 is better. Its fade level is 3-4. The color fastness to acrylic, polyester and acetate can reach 4 or above. For cotton and wool, the color fastness of nylon is also 3-4. The above results show that the present invention can obtain a good anhydrous dyeing effect on the sample of Example 1.
  • Table 3 and Table 4 are the experimental results of using the method described in this example to dye 1g of pure cotton fiber with disperse reactive yellow dye (o.m.f is 5%).
  • 2.5g / L of saturated steam was introduced into the cage for pretreatment, and 10ml of methanol was added to the dye dissolution unit to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa supercritical carbon dioxide fluid.
  • the fluid static dyeing cycle is every 1min after 1min, the dyeing temperature is 120 °C, the bath ratio is 1: 2000, and the total dyeing time is 60min.
  • the online cleaning temperature is 80 °C, the pressure is 20Mpa, and the total cleaning time is 30min.
  • Table 3 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 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 3 also shows that the standard deviation of the color depth value of the sample surface of Example 2 is also small, which The value is 0.022, indicating that the inventive technique has excellent levelness on the sample of Example 2.
  • Table 4 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample of Example 2 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. The above results indicate that the present invention can also obtain a good anhydrous dyeing effect on the sample of Example 2.
  • Table 5 and Table 6 are the experimental results of using the method described in this example to perform dyeing processing on 1 g of pure cotton fiber with a dispersed reactive yellow dye (o.m.f is 2%).
  • a dispersed reactive yellow dye o.m.f is 2%.
  • 5 g / L of saturated steam was introduced into the cage for pretreatment, and 15 ml of acetone was added to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa supercritical carbon dioxide fluid.
  • the fluid static dyeing cycle is 1 minute after every 5min, the dyeing temperature is 130 °C, the bath ratio is 1: 2000, and the total dyeing time is 40min.
  • the online cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the total cleaning time is 30min.
  • the experimental results in Table 5 show that, by using the anhydrous fiber dyeing method of the present invention, the reactive disperse yellow dye can dye the dry cotton fibers under the experimental conditions to obtain a good dyeing effect.
  • the hue angle h ° of the sample is 88.97, the yellow shade is more pure, the color is more vivid, and the C * value is increased to 24.42.
  • the sample of Example 3 is also under the same large proportion of fluid conditions, and its surface color depth value It can also reach 1.264, which also proves that the sample of Example 3 after pretreatment has good dyeing and fixing properties.
  • Table 5 also shows that the standard deviation of the surface color depth value of the sample of Example 3 is also small. The value is 0.056, indicating that the leveling property of the technology of the present invention on the sample of Example 3 is also very good.
  • Table 6 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample in Example 3 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. The above results indicate that the present invention can also obtain a good anhydrous dyeing effect on the sample of Example 3.
  • Table 7 and Table 8 are the experimental results of using the method described in this example to dye 1 g of pure cotton fiber with a disperse reactive red dye (o.m.f is 2%).
  • a disperse reactive red dye o.m.f is 2%.
  • 5 g / L of saturated steam was introduced into the cage for pretreatment, and 15 ml of acetone was added to pre-dissolve the dye.
  • the dyeing and dyeing conditions are 20Mpa supercritical carbon dioxide fluid.
  • the fluid static dyeing is circulated for 1min after every 5min, the dyeing temperature is 130 °C, the bath ratio is 1: 2000, and the total dyeing time is 90min.
  • the online cleaning temperature is 80 °C
  • the pressure is 20Mpa
  • the total cleaning time is 30min.
  • Table 7 show that with 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 of the sample is 1.59, the red color is also more pure, the color is more vivid, and the C * value is increased to 23.53.
  • the sample of Example 4 is also under the same large proportion of fluid conditions, and its surface color depth value It can also reach 1.276, which also proves that the sample of Example 4 after pretreatment has good dyeing and fixing properties.
  • Table 7 also shows that the standard deviation of the surface color depth value of the sample of Example 4 is also small. The value is 0.029, which indicates that the leveling property of the technology of the present invention on the sample of Example 4 is also very good.
  • Table 8 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample in Example 4 is also excellent. 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 4.
  • Table 9 and Table 10 are the experimental results of using the method described in this example to dye 1 g of pure cotton fiber with a disperse reactive red dye (o.m.f is 2%).
  • a disperse reactive red dye o.m.f is 2%.
  • the dyeing and dyeing conditions are 20Mpa supercritical carbon dioxide fluid.
  • the fluid static dyeing cycle is every 1min after 1min, the dyeing temperature is 120 °C, the bath ratio is 1: 2000, and the total dyeing time is 60min.
  • the online cleaning temperature is 80 °C, the pressure is 20Mpa, and the total cleaning time is 30min.
  • Table 9 show that, using the anhydrous fiber dyeing method of the present invention, a good dyeing effect can be obtained by dyeing dry cotton fibers with a reactive disperse yellow dye.
  • the C * value is increased to 30.63, the color is more vivid.
  • the sample of Example 5 is also under the same large proportion of fluid conditions, and its surface color depth value It can also reach 1.494, which also proves that the sample of Example 5 has good dyeing and fixing properties.
  • Table 9 also shows that the standard deviation of the color depth value of the sample surface of Example 5 is also small, which The value is 0.012, indicating that the water dyeing sample in Example 5 has excellent levelness.
  • Table 10 shows that with the anhydrous fiber dyeing method of the present invention, the conventional color fastness of the sample in Example 5 is also excellent. Its fade fastness grade is 4 grades. 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 show that the present invention can also obtain a good anhydrous fiber dyeing effect under the experimental conditions of Example 5.

Landscapes

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

Abstract

本发明公开了一种以超临界二氧化碳流体为介质的无水纤染方法，属于纺织染整加工技术领域。本发明干态纤维通过机械压紧的方式在特制多孔纱笼中以层状形式进行紧密装填，使纤维在装置内结构紧密，分布均匀，通过预处理，来提高其染色性能。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。在使用专用染料对超临界CO 2染色时，用本发明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。本发明过程简单，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。

Description

一种以超临界二氧化碳流体为介质的无水纤染方法 技术领域
本发明涉及一种以超临界二氧化碳流体为介质的无水纤染方法，属于纺织染整加工技术领域。
背景技术
超临界CO 2流体(Supercritical Carbon Dioxide Fluid，SCF-CO 2)代替水作为染色介质，并且工艺流程短、操作方便、不产生工业上的废水污染，彻底的解决了因纺织品加工所带来的环境污染所造成的问题。超临界CO 2具有部分气体的性质，黏度很小，扩散系数高，扩散边界小，缩短染色时间。并且，在染色处理后，流体可以通过气态的形式放出来，实现了残留固体染料和气体的回收利用，不需要进行染色后的烘干处理，可以少加或者不加染料助剂，实现了资源的最优化利用，保护了生态环境。
目前，超临界二氧化碳无水染色在涤纶、锦纶、醋酯、腈纶、丙纶的织物或筒子纱形式，已有较多研究和探讨，并可达到令人满意的效果。然而，对占较大份额的亲水性天然短纤如棉、羊毛，以及其他合成纤维短纤，在超临界CO 2流体中无水纤染技术的研究相对较少。
特别地，在传统水浴中，很容易实现天然短纤的膨胀和染料的扩散，从而获得较满意的染色效果。而在疏水性超临界二氧化碳流体中，如何打开短纤大分子链间的氢键，创造染料上染的必要条件，以及如何提高染料活性基与短纤上官能团的反应或/及固着，是超临界二氧化碳流体中实现无水纤染的关键问题。
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 供一种以超临界二氧化碳流体为介质的无水纤染方法。
本发明的第一个目的是提供一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，包括如下步骤：
(1)将干态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干态踩“棉”或装填；
(2)将上述步骤(1)中完成踩“棉”或装填的纱笼置于高压染缸中进行预处理；
(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)保温染色结束后，利用干净的超临界二氧化碳介质对染色系统进行降温，且当系统温度降低至一定温度时，再在一定条件下进行在线浮色清洗，最后对染色系统中流体介质进行回收，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，所述的干态纤维，为天然纤维中的短纤如棉花，或经加工后的麻类散纤，或者为合成纤维如粘胶、涤纶、锦纶、腈纶经加工成的短纤。
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，对蓬松的棉花进行整齐、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。
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若干镂空的小孔。
进一步的，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”。
进一步的，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(2)中预处理介质，可以为饱和蒸汽、过热蒸汽，或其他极性溶剂中的一种或者几种。
进一步的，所述步骤(2)中预处理的主要条件为压力0-1Mpa，时间 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，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，所述的系统温度降低至一定温度，其温度为30-100℃。
进一步的，在步骤(4)中，所述的一定条件下的在线浮色清洗，其工艺条件为，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，通过回收系统将二氧化碳进行分离、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。
本发明的技术方案如下：在本发明中，干态纤维通过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装填，使纤维在装置内结构紧密，分布均匀，通过一定介质的预处理，来提高其染色性能。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。
借由上述方案，本发明至少具有以下优点：
在使用专用染料对超临界CO 2染色时，用本发明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，且能获得教好的染色效果。本发明 过程简单，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。
附图说明
图1是本发明提供的超临界二氧化碳流体中织物染色的系统原理图；
其中：1、CO 2储罐；2、截止阀；3、冷凝器；4、加压泵；5、预热器；6、截止阀；7、染料溶解单元；8、过滤器；9、截止阀；10、纤染染缸；11、截止阀；11’、截止阀；12、循环泵；12’、气体回收泵；13、截止阀；14、截止阀；15、微调阀；16、温度计；17、压力表；18、分离釜；19、温度计；20、压力表；21、净化器；
图2为纤染染缸的剖面图，其中：①、流体和染料入口；②、非二氧化碳介质入口截止阀；③、(多孔)纱笼；④、流体出口；⑤、快开结构；⑥、染缸密封盖；⑦、非二氧化碳介质入口；⑧、接口。
具体实施方式
本发明将根据具体事例做进一步的描述，但其仅为例证性的目的而不祈祷限制性作用。本领域技术人员可由本说明书所解释的内容清楚的了解本发明的特点与功效，本发明还可以通过另外不同的具体实施方式加以实施或运用。实施例中未说明具体条件的实验，通常按照常规条件如厂商说明书、实验指南或教科书内容的条件。
本发明实施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超临界二氧化碳流体无水纤染步骤为如下：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非二氧化碳介质(如饱和蒸汽等)，并调节系统中截止阀11’的开合度，保持染缸内的一定压力为0-1.0Mpa，对纤维进行预处理5～180min。预处理结束后，关闭非CO 2介质入口截止阀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，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。使溶解染料随流体循环，并与待染纤维充分上染。染料上染过程中流体循环时间与流体静态时间比为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流体进行分离和回收。
流体分离回收结束后，再次重复上述操作对纤维进行在线清洗，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，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，用活性分散染料对短纤进行染色，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型分光测色仪对超临界CO2流体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D65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 PCTCN2018114040-appb-000001
来衡量，计算方式如(1)所示。
Figure PCTCN2018114040-appb-000002
Figure PCTCN2018114040-appb-000003
其中，i代表第i个测试点(i＝1,2,3,…..,n；此处n＝8)；
Figure PCTCN2018114040-appb-000004
代表第i个测试点在最大吸收波长处的表面色深值；
Figure PCTCN2018114040-appb-000005
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对超临界CO 2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和表2是采用本实施例所述方法，对1g纯棉纤维采用分散活性黄染料(o.m.f为5％)进行染色加工的实验结果。染色前通入2.5g/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10ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界二氧化碳流体，流体静态染色每5min后循环1min，染色温度120℃，浴比为1:2000，总的上染时间为60min。染色结束后，在线清洗温度为80℃，压力为20Mpa，总清洗时间为30min。
表1 实施例1样品颜色特征值的测定及匀染性评价
Figure PCTCN2018114040-appb-000006
表2 实施例1样品的耐水洗牢度评价
Figure PCTCN2018114040-appb-000007
表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1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 PCTCN2018114040-appb-000008
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还表明，实施例1样品表面色深值的标准差较小，其
Figure PCTCN2018114040-appb-000009
值为0.045，表明实施例1样品匀染性优良。
表2显示，采用本发明的无水纤染方法，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。上述结果表明，本发明能在实施例1样品上获得良好的无水染色效果。
实施例2：
表3和表4是采用本实施例所述方法，对1g纯棉纤维采用分散活性黄染料(o.m.f为5％)进行染色加工的实验结果。染色前通入2.5g/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10ml甲醇对染料进行预溶解。染色上染条件为20Mpa超临界二氧化碳流体，流体静态染色每5min后循环1min，染色温度120℃，浴比为1:2000，总的上染时间为60min。染色结束后，在线清洗温度为80℃，压力为20Mpa，总清洗时间为30min。
表3 实施例2样品颜色特征值的测定及匀染性评价
Figure PCTCN2018114040-appb-000010
表4 实施例2样品的耐水洗牢度评价
Figure PCTCN2018114040-appb-000011
表3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 PCTCN2018114040-appb-000012
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3还表明，实施例2样品表面色深值的标准差也较小，其
Figure PCTCN2018114040-appb-000013
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4显示，采用本发明的无水纤染方法，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。上述结果表明，本发明也能在实施例2样品上获得良好的无水染色效果。
实施例3：
表5和表6是采用本实施例所述方法，对1g纯棉纤维采用分散活性黄染料(o.m.f为2％)进行染色加工的实验结果。染色前通入5g/L的饱和蒸汽在纱笼中进行预处理，并加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界二氧化碳流体，流体静态染色每5min后循环1min，染色温度130℃，浴比为1:2000，总的上染时间为40min。染色结束后，在线清洗温度为80℃，压力为20Mpa，总清洗时间为30min。
表5 实施例3样品颜色特征值的测定及匀染性评价
Figure PCTCN2018114040-appb-000014
表6 实施例3样品的耐水洗牢度评价
Figure PCTCN2018114040-appb-000015
表5中实验结果显示，采用本发明的无水纤染方法，活性分散黄染料染色在该实验条件下的干态棉纤维可获得良好的染色效果。其样品的色相角h°为88.97，其黄色色光也较为纯正，颜色更为鲜艳，C*值增大为24.42。同时，实施例3样品也在相同大比例流体条件下，其表面色深值
Figure PCTCN2018114040-appb-000016
也可达到1.264，同样证明了经过预处理后的实施例3样品有良好的上染和固着性能。同时，表5还表明，实施例3样品表面色深值的标准差也较小，其
Figure PCTCN2018114040-appb-000017
值为0.056，表明本发明技术在实施例3样品上的匀染性也非常优良。
表6显示，采用本发明的无水纤染方法，实施例3中的样品常规色牢度也较好。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。上述结果表明，本发明也能在实施例3样品上获得良好的无水染色效果。
实施例4：
表7和表8是采用本实施例所述方法，对1g纯棉纤维采用一种分散活性红染料(o.m.f为2％)进行染色加工的实验结果。染色前通入5g/L的饱和蒸汽在纱笼中进行预处理，并加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界二氧化碳流体，流体静态染色每5min后循环1min，染色温度130℃，浴比为1:2000，总的上染时间为90min。染色结束后，在线清洗温度为80℃，压力为20Mpa，总清洗时间为30min。
表7 实施例4样品颜色特征值的测定及匀染性评价
Figure PCTCN2018114040-appb-000018
表8 实施例4样品的耐水洗牢度评价
Figure PCTCN2018114040-appb-000019
表7中的相关实验结果显示，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。其样品的色相角h°为1.59，其红色色光也较为纯正，颜色更为鲜艳，C*值增大为23.53。同时，实施例4样品也在相同大比例流体条件下，其表面色深值
Figure PCTCN2018114040-appb-000020
也可达到1.276，同样证明了经过预处理后的实施例4样品有良好的上染和固着性能。同时，表7还表明，实施例4样品表面色深值的标准差也较小，其
Figure PCTCN2018114040-appb-000021
值为0.029，表明本发明技术在实施例4样品上的匀染性也非常优良。
表8显示，采用本发明的无水纤染方法，实施例4中样品的常规色牢度也较优良。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4样品上获得良好的无水染色效果。
实施例5：
表9和表10是采用本实施例所述方法，对1g纯棉纤维采用一种分散活性红染料(o.m.f为2％)进行染色加工的实验结果。染色前通入2.5g/L的饱和蒸汽在纱笼中进行预处理，并加入15ml丙酮对染料进行预溶解。染色上染条件为20Mpa超临界二氧化碳流体，流体静态染色每5min后循环1min，染色温度120℃，浴比为1:2000，总的上染时间为60min。染色结束后，在线清洗温度为80℃，压力为20Mpa，总清洗时间为30min。
表9 实施例5样品颜色特征值的测定及匀染性评价
Figure PCTCN2018114040-appb-000022
表10 实施例5样品的耐水洗牢度评价
Figure PCTCN2018114040-appb-000023
表9中的相关实验结果显示，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。其样品的色相角h°为85.87，λ max＝405nm，其色调为黄色。其C*值增大为30.63，颜色较为鲜艳。此外，实施例5样品也在相同大比例流体条件下，其表面色深值
Figure PCTCN2018114040-appb-000024
也可达到1.494，同样证明了实施例5样品具有良好的上染和固着性能。同时，表9还表明，实施例5样品表面色深值的标准差也较小，其
Figure PCTCN2018114040-appb-000025
值为0.012，表明实施例5中的无水纤染样品匀染性也非常优良。
表10显示，采用本发明的无水纤染方法，实施例5中样品的常规色牢度也较为优良。其褪色牢度级数在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。上述结果显示，本发明也能在实施例5的实验条件下，获得良好的无水纤染效果。
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. 一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，包括如下步骤：
    (1)将干态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干态踩“棉”或装填；
    (2)将上述步骤(1)中完成踩“棉”或装填的纱笼置于高压染缸中进行预处理；
    (3)在上述步骤(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)保温染色结束后，利用干净的超临界二氧化碳介质对染色系统进行降温，且当系统温度降低至一定温度时，再在一定条件下进行在线浮色清洗，最后对染色系统中流体介质进行回收，完成超临界二氧化碳流体介质中的无水纤染加工。
  2. 根据权利要求1所述的一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，所述的干态纤维，为天然纤维中的短纤如棉花，或经加工后的麻类散纤，或者为合成纤维如粘胶、涤纶、锦纶、腈纶经加工成的短纤。
  3. 根据权利要求1所述的一种以超临界二氧化碳流体为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，对蓬松的棉花进行整齐、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。
  4. 根据权利要求1所述的一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，所述步骤(1)中特制多孔纱笼，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若干镂空的小孔。
  5. 根据权利要求1所述的一种以超临界二氧化碳流体为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”。
  6. 根据权利要求1所述的一种以超临界二氧化碳流体为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纱笼中“踩棉”时，其一定紧密度为50-300kg/m 3。
  7. 根据权利要求1所述的一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，所述步骤(2)中预处理介质，为饱和蒸汽、过热蒸汽或其他极性溶剂中的一种或者几种。
  8. 根据权利要求1所述的一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，所述步骤(2)中预处理的主要条件为压力0-1Mpa，时间5～180min。
  9. 根据权利要求1所述的一种以超临界二氧化碳流体为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、烟酸结构中的一种或几种，或他们的衍生化合物。
  10. 根据权利要求1所述的一种以超临界二氧化碳流体为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。
  11. 根据权利要求10所述的一种以超临界二氧化碳流体为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，可以为1:5～5:1。
  12. 根据权利要求1所述的一种以超临界二氧化碳流体为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。
  13. 根据权利要求1所述的一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，在步骤(4)中，所述的系统温度降低至一定温度，其温度为30-100℃。
  14. 根据权利要求1所述的一种以超临界二氧化碳流体为介质的无水纤染方法，其特征在于，在步骤(4)中，所述的一定条件下的在线浮色清洗，其工 艺条件为，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1所述的一种以超临界二氧化碳流体为介质的无水纤染方法,其特征在于：在步骤(4)中，染色完成后，通过回收系统将二氧化碳进行分离、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/CN2018/114040 2018-10-16 2018-11-06 一种以超临界二氧化碳流体为介质的无水纤染方法 Ceased WO2020077702A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/346,244 US11608592B2 (en) 2018-10-16 2018-11-06 Fiber dyeing method using supercritical carbon dioxide fluid as medium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811202696.0A CN109355929A (zh) 2018-10-16 2018-10-16 一种以超临界二氧化碳流体为介质的无水纤染方法
CN201811202696.0 2018-10-16

Publications (1)

Publication Number Publication Date
WO2020077702A1 true WO2020077702A1 (zh) 2020-04-23

Family

ID=65349188

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/114040 Ceased WO2020077702A1 (zh) 2018-10-16 2018-11-06 一种以超临界二氧化碳流体为介质的无水纤染方法

Country Status (3)

Country Link
US (1) US11608592B2 (zh)
CN (1) CN109355929A (zh)
WO (1) WO2020077702A1 (zh)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110670382B (zh) * 2019-09-28 2022-01-11 桐乡市鑫隆印染有限公司 一种厚型涤纶纺织品柔性化无水印染的方法
CN110565415A (zh) * 2019-10-11 2019-12-13 上海复璐帝流体技术有限公司 一种超临界二氧化碳印染工艺及其印染系统
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
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
WO2021237519A1 (zh) * 2020-05-27 2021-12-02 南通纺织丝绸产业技术研究院 一种用于天然纤维超临界co2流体闪爆处理的方法
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
CN112267317B (zh) * 2020-11-02 2022-12-02 山东高棉智能纤染科技有限公司 一种黏胶纤维无水染色方法及系统
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
CN113046957B (zh) * 2021-03-12 2023-05-26 辽宁轻工职业学院 一种羽毛纤维超临界co2无水染色装置及其染色方法
CN114481631A (zh) * 2022-01-25 2022-05-13 苏州大学 一种以超临界流体为介质的纺织品三防整理方法
CN115045127B (zh) * 2022-07-28 2023-08-01 河南水工智造科技有限公司 一种节能环保锦纶纤维超流体染色工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300588A (ja) * 2003-03-28 2004-10-28 Howa Kk 繊維の染色方法およびその染色物
CN101091017A (zh) * 2004-11-04 2007-12-19 费伊肯开发与实施有限公司 在超临界或近临界二氧化碳中用活性染料对基质染色的方法
WO2015032020A1 (zh) * 2013-09-03 2015-03-12 苏州大学 纺织品的一种相转移催化固色加工方法
CN104562759A (zh) * 2013-10-29 2015-04-29 李长娟 散纤维染色工艺
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
CN106468026A (zh) * 2015-08-18 2017-03-01 香港纺织及成衣研发中心有限公司 用于超临界co2流体染色的棉纤维染料及其染色方法
CN108442058A (zh) * 2018-04-04 2018-08-24 华尔科技集团股份有限公司 染色纱笼

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1014395C2 (nl) * 2000-02-16 2001-08-20 Stork Brabant Bv Werkwijze voor het verven van textielmaterialen in een superkritisch flu´dum.
CN102296469B (zh) * 2011-07-07 2013-05-08 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
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
CN103726351B (zh) * 2013-12-30 2016-01-20 成都纺织高等专科学校 一种超临界co2流体还原染料染色方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300588A (ja) * 2003-03-28 2004-10-28 Howa Kk 繊維の染色方法およびその染色物
CN101091017A (zh) * 2004-11-04 2007-12-19 费伊肯开发与实施有限公司 在超临界或近临界二氧化碳中用活性染料对基质染色的方法
WO2015032020A1 (zh) * 2013-09-03 2015-03-12 苏州大学 纺织品的一种相转移催化固色加工方法
CN104562759A (zh) * 2013-10-29 2015-04-29 李长娟 散纤维染色工艺
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
CN106468026A (zh) * 2015-08-18 2017-03-01 香港纺织及成衣研发中心有限公司 用于超临界co2流体染色的棉纤维染料及其染色方法
CN108442058A (zh) * 2018-04-04 2018-08-24 华尔科技集团股份有限公司 染色纱笼

Also Published As

Publication number Publication date
US20210355632A1 (en) 2021-11-18
US11608592B2 (en) 2023-03-21
CN109355929A (zh) 2019-02-19

Similar Documents

Publication Publication Date Title
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
CN102296469B (zh) 在超临界二氧化碳流体中天然纤维的染色方法
WO2020077665A1 (zh) 一种混合流体介质的无水纤染方法
CN105113162A (zh) 一种节能减排的纤维制品续缸染色系统及其染色方法
CN103469623B (zh) 一种活性染料对未煮漂棉纺织品进行无盐染色的方法
CN102392367B (zh) 在低压二氧化碳介质中活性分散染料的固色方法
CN104674569A (zh) 一种纤维素纤维织物的天然染料染色方法
CN101858019A (zh) 一种家纺面料的湿态汽蒸高效连续染色工艺方法
CN105040317B (zh) 一种超临界二氧化碳经轴染色架、染色釜及染色方法
CN111535017B (zh) 一种用于天然纤维超临界co2流体闪爆处理的方法
CN111472182A (zh) 一种高温高压少水染色工艺
CN104611948B (zh) 丝线用同浴恒温吸附染色方法
CN107904986B (zh) 超临界co2流体天然纺织染料组合物及染色方法
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
CN109056392A (zh) 一种天然染料的染色方法
CN112430399B (zh) 红花黄色素及其制备方法和染色方法
CN104233885B (zh) 一种涤棉仿丝绸织物的活性印花方法
CN203228293U (zh) 竹材碳化染色连续加工装备
CN113152122B (zh) 一种红色偶联型分散染料复配物及其染色工艺
CN103669044A (zh) 一种牦牛绒散纤维超临界二氧化碳染色工艺方法
CN101117775A (zh) 黄菊花染料染丝光羊毛或丝光毛织物的方法
CN112111887A (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
CN104846664A (zh) 一种改性罗布麻纤维的酸性染料染色方法
CN107524024A (zh) 一种在低浴比下解决活性翠兰染料聚集色花的方法

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: 18937515

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: 18937515

Country of ref document: EP

Kind code of ref document: A1