CN101368343B - Supercritical CO2 mediated color matching and dyeing method - Google Patents
Supercritical CO2 mediated color matching and dyeing method Download PDFInfo
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- CN101368343B CN101368343B CN2008101214515A CN200810121451A CN101368343B CN 101368343 B CN101368343 B CN 101368343B CN 2008101214515 A CN2008101214515 A CN 2008101214515A CN 200810121451 A CN200810121451 A CN 200810121451A CN 101368343 B CN101368343 B CN 101368343B
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Abstract
The invention discloses a combination dyeing method which takes supercritical CO2 as medium, including the following steps: with supercritical CO2 fluid as medium, dyeing the fabrics for being dyed respectively with different disperse dyes and enabling the dyed fabrics to have desirable colors. The invention has the advantages that the invention provides an effective combination dyeing method with supercritical CO2 as medium, and the combination dyeing method is widely applicable to the printing and dyeing industries and has obvious social and economic benefits.
Description
(1) technical field
The present invention relates to a kind of supercritical CO
2The combination dyeing method of mediation, this method has realized the colorant match in the dyeing course in the supercritical carbon dioxide.
(2) background technology
As dyeing medium, there are problems such as water consumption is big, energy consumption is high, environmental pollution is serious with water in traditional dyeing technology.China is first big country of textile printing and dyeing, and the dyeing waste water of textile printing and dyeing industry discharging is one of major polluting sources in China's industrial system.The supercritical fluid dyeing of development in recent years, with traditional be that the dyeing of medium is compared to have and polluted advantages such as little, that cost is low, operation is few with water, be a kind of " green dyeing " technology that has a extensive future.
Supercritical carbon-dioxicle dyeing method has been introduced the supercritical fluid technique of chemical process, utilize carbon dioxide as dyeing medium dyestuff dissolving and deliver to the fiber hole, carbon dioxide can fully separate with dyestuff again after dyeing finishes, whole dyeing course carries out in sealing system, do not produce waste water and waste gas, belong to the process of green production, meet STRATEGIES OF SUSTAINABLE DEVELOPMENT.Some scholars study supercritical CO 2 dyeing with diverse ways and equipment both at home and abroad, have obtained certain achievement.But because the difference and the limitation of experimental technique and equipment, most of research all is limited to single supercritical CO 2 dyeing of planting dyestuff, but in order to make textiles can obtain desirable color and coloured light, be not enough only, dyes in different colors need be pieced together mix and carry out combination dyeing with dying on single kind dyestuff.
Traditional immersion method combination dyeing technology is to prepare dye bath with two or more dyestuff by proper proportion, and fabric is dyeed, to obtain the Color of expection.Supercritical CO
2Dyeing generally is placed on dyestuff dyestuff still, supercritical CO
2Earlier through the dyestuff still, dyestuff is dissolved in wherein, and enters dyeing caldron thereupon fabric is dyeed.Because dyestuff is at supercritical CO
2In solubility less, usually the consumption of dyestuff is with respect to supercritical CO
2Solubility is excessive.On the other hand, because under uniform temperature and pressure, every kind of dyestuff is at supercritical CO
2In solubility be certain, be dissolved in supercritical CO like this
2In and the ratio that thereupon enters the mixed dye of dyeing caldron also be certain.Thereby the Color that can not expect with acquisition by the ratio of adjusting mixed dye simply.Even mixed dye is directly placed dyeing caldron, because dyestuff also is to be dissolved in supercritical CO earlier
2In, and then fabric dyeed, therefore also there is same problem.
(3) summary of the invention
The object of the invention provides a kind of supercritical CO
2The combination dyeing method of mediation.
The technical solution used in the present invention is:
A kind of supercritical CO
2The combination dyeing method of mediation, described method comprises: with supercritical CO
2Fluid is a medium, and successively the fabric for the treatment of dyeing with DISPERSE DYES not of the same race dyes, and makes by the dyeing and weaving thing and obtains needed color.
The present invention is the many baths method colorant match method in the supercritical CO 2 dyeing.Dyeing medium in this method is a supercritical carbon dioxide, dyestuff is any dyestuff that can be applied to supercritical dyeing, by the dyeing and weaving thing is synthetic fiber and natural fabric, and the dyeing apparatus of employing is a supercritical carbon dioxide dyeing cycle device, and the colouring method of employing is a running balancing.Described many baths of combination dyeing process using method is about to fabric and successively is positioned in the coloring system of different dyes, carries out obtaining finished product after the dyeing more than twice or twice.
Carbon dioxide is a nonpolar molecule, can only dissolve dyestuff nonpolar or that polarity is low.In dyeing course, dyestuff at first is dissolved in the supercritical carbon dioxide fluid, the dyestuff of dissolving enters the close fiber interface of Dynamic Boundary layer (being difficult to flow) behind certain distance near fiber interface → dyestuff gradually with flowing of dye liquor, mainly rapidly will be to fibrous inside diffusion transfer (inside and outside consumption difference or the inside and outside dyestuff chemistry potential difference of producing of fiber) by fiber surface absorption (molecular force between them is enough big) → dyestuff near fiber → dyestuff by the diffusion of self.
When the present invention uses dyestuff more than 2 kinds and dyes, be will be to be dyeed the fabric dyestuff gradation dyeing that places different color and lusters successively respectively, the described method of described gradation staining procedure is as follows: will treat that the dyeing and weaving thing places the dyeing system of first kind of dyestuff to carry out the dyeing first time, after dyeing finishes for the first time, the fabric that is colored places the dyeing system of second kind of dyestuff to carry out the dyeing second time again, obtains the fabric of combination dyeing; If necessary, after dyeing finishes for the second time, fabric can be placed the dyeing system of the third dyestuff dye for the third time, obtain needed color up to fabric;
Described dyeing system is the closed-cycle system that dyeing caldron, dyestuff still and circulating pump are formed;
The described dyeing first time is with colouring method is as follows for the second time: DISPERSE DYES is placed the dyestuff still, treat that the dyeing and weaving thing places dyeing caldron, liquid carbon dioxide is injected dyeing system, under 70～140 ℃, 14～30MPa, the ON cycle pump carries out dyeing cycle to fabric, dyeing time is 30～120min, and the fluid mass flow is 100～120kg/h.
Preferably, described first kind of dyestuff and second kind of dyestuff are in disperse red 343, disperse blue 366, the disperse yellow 241 any two kinds.The described dyeing and weaving thing for the treatment of is a dacron.
Beneficial effect of the present invention is mainly reflected in:
1, a kind of method of effective supercritical carbon dioxide combination dyeing is provided, and this method has solved mixed dye at supercritical CO
2In the ratio of dissolving simultaneously non-adjustable and can't carry out the problem of colorant match, by the dyeing more than 2 times or 2 times, finally obtain the combination dyeing effect of expecting.
2, by control dyeing condition (time, temperature, pressure), the control of the amount of dying on the dyestuff in can realizing easily each is bathed, thereby by regulate respectively bathe dyestuff on the ratio of dying make fabric obtain needed color.
3, can obtain Color preferably, dye the water-fast of back fabric and wash COLOR FASTNESS and colour fastness to rubbing all satisfies national standard.
(4) description of drawings
The dyeing cycle equipment schematic diagram that Fig. 1 adopts for many baths of supercritical carbon dioxide method combination dyeing method of the present invention.
(5) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Supercritical carbon dioxide dyeing cycle of the present invention system is referring to Fig. 1, comprise the carbon dioxide steel cylinder 1, carbon dioxide storage tank 2, refrigeration system 3, force (forcing) pump 4, dyestuff still 5, dyeing caldron 6, circulating pump 7 and the separating still 8 that link to each other successively, ST1～ST13 is a valve.
The DISPERSE DYES (powder does not add any auxiliary agent) that dye adopts Zhejiang dying of Jiangjiang two factories to produce, with purity be 99% carbon dioxide as the supercritical dyeing medium, usefulness commodity dacron carries out supercritical fluid two bath method combination dyeings as pollutant.
Dyeing is:
A. disperse red 3430.1g is preset in the dyestuff still, (400mm * 180mm) is preset in dyeing caldron by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 110 ℃, 20MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 60min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system, taking-up is by the dyeing and weaving thing, clean coloring system simultaneously and (overlap the overcritical combination dyeing technology that above dye cycle device is formed if adopt by two covers or two with residual dye in the removal system, in each cover dyeing device, add dyes in different colors respectively and replace dyeing, then do not need coloring system is cleaned after each dyeing finishes, improved dyeing efficient greatly).
D, disperse blue 3660.1g is placed in the dyestuff still, to by dyeing and weaving thing dual-staining step B (dyeing condition changes into: 90 ℃ of temperature, pressure 18Mpa, dyeing time 40min) and staining procedure C.
After E, dyeing are finished, obtain reddish violet cloth sample.
Embodiment 2:
A. disperse red 3430.1g is preset in the dyestuff still, (400mm * 180mm) is preset in dyeing caldron by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 90 ℃, 18MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 40min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system, taking-up is by the dyeing and weaving thing, clean coloring system simultaneously and (overlap the overcritical combination dyeing technology that above dye cycle device is formed if adopt by two covers or two with residual dye in the removal system, in each cover dyeing device, add dyes in different colors respectively and replace dyeing, then do not need coloring system is cleaned after each dyeing finishes, improved dyeing efficient greatly).
D, disperse blue 3660.1g is placed in the dyestuff still, to by dyeing and weaving thing dual-staining step B (dyeing condition changes into: 110 ℃ of temperature, pressure 20Mpa, dyeing time 60min) and staining procedure C.
After E, dyeing are finished, obtain bluish violet cloth sample.
Embodiment 3:
A. disperse red 3430.1g is preset in the dyestuff still, (400mm * 180mm) is preset in dyeing caldron by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 110 ℃, 20MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 60min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system, taking-up is by the dyeing and weaving thing, clean coloring system simultaneously and (overlap the overcritical combination dyeing technology that above dye cycle device is formed if adopt by two covers or two with residual dye in the removal system, in each cover dyeing device, add dyes in different colors respectively and replace dyeing, then do not need coloring system is cleaned after each dyeing finishes, improved dyeing efficient greatly).
D, disperse yellow 2410.1g is placed in the dyestuff still, to by dyeing and weaving thing dual-staining step B (dyeing condition changes into: 90 ℃ of temperature, pressure 18Mpa, dyeing time 40min) and staining procedure C.
After E, dyeing are finished, obtain orange red cloth sample.
Embodiment 4:
A. disperse red 3430.1g is preset in the dyestuff still, (400mm * 180mm) is preset in dyeing caldron by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 90 ℃, 18MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 40min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system, taking-up is by the dyeing and weaving thing, clean coloring system simultaneously and (overlap the overcritical combination dyeing technology that above dye cycle device is formed if adopt by two covers or two with residual dye in the removal system, in each cover dyeing device, add dyes in different colors respectively and replace dyeing, then do not need coloring system is cleaned after each dyeing finishes, improved dyeing efficient greatly).
D, disperse yellow 2410.1g is placed in the dyestuff still, to by dyeing and weaving thing dual-staining step B (dyeing condition changes into: 110 ℃ of temperature, pressure 20Mpa, dyeing time 60min) and staining procedure C.
After E, dyeing are finished, obtain orange-yellow cloth sample.
Embodiment 5:
A. disperse blue 3660.1g is preset in the dyestuff still, (400mm * 180mm) is preset in dyeing caldron by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 110 ℃, 20MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 60min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system, taking-up is by the dyeing and weaving thing, clean coloring system simultaneously and (overlap the overcritical combination dyeing technology that above dye cycle device is formed if adopt by two covers or two with residual dye in the removal system, in each cover dyeing device, add dyes in different colors respectively and replace dyeing, then do not need coloring system is cleaned after each dyeing finishes, improved dyeing efficient greatly).
D, disperse yellow 2410.1g is placed in the dyestuff still, to by dyeing and weaving thing dual-staining step B (dyeing condition changes into: 90 ℃ of temperature, pressure 18Mpa, dyeing time 40min) and staining procedure C.
After E, dyeing are finished, obtain aquamarine blue cloth sample.
Embodiment 6:
A. disperse blue 3660.1g is preset in the dyestuff still, (400mm * 180mm) is preset in dyeing caldron by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 90 ℃, 18MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 40min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system, taking-up is by the dyeing and weaving thing, clean coloring system simultaneously and (overlap the overcritical combination dyeing technology that above dye cycle device is formed if adopt by two covers or two with residual dye in the removal system, in each cover dyeing device, add dyes in different colors respectively and replace dyeing, then do not need coloring system is cleaned after each dyeing finishes, improved dyeing efficient greatly).
D, disperse yellow 2410.1g is placed in the dyestuff still, to by dyeing and weaving thing dual-staining step B (dyeing condition changes into: 110 ℃ of temperature, pressure 20Mpa, dyeing time 60min) and staining procedure C.
After E, dyeing are finished, obtain yellow green cloth sample.
Embodiment 7 (Comparative Examples):
A. will be preset in the dyestuff still after 0.1g disperse red 343 and 366 mixing of 0.1g disperse blue, (400mm * 180mm) be preset in dyeing caldron carries out one-bath dyeing by dyeing and weaving thing terylene;
B. before the dyeing, close exhaust-valve ST7, ST8 and ST5, ST10, ST13, open ST1, ST2, ST3, ST4, ST6 and ST9; Start force (forcing) pump, open heater, to system's intensification of pressurizeing; After arriving 110 ℃, 20MPa, close ST2, ST6, open ST5, the ON cycle pump carries out dyeing cycle, keeps temperature and pressure in the dyeing system, and control fluid mass flow is 100kg/h, and the dyeing cycle time is 60min.
C. after dyeing finishes, close the closed circuit between dyestuff still and dyeing caldron, close heater simultaneously, in dyeing caldron, feed fresh CO
2Make dyeing caldron keep certain pressure, utilize circulating pump supercritical CO
2In dyeing caldron, constantly circulate, clean by the dyeing and weaving thing surface loose colour of set not.Clean and finish, open ST10, make in the dyeing system carbon dioxide by separating still be recovered to carbon dioxide storage tank after excess dye is separated, close ST10, open exhaust-valve ST4 and ST8, residual carbon dioxide in the emptying dyeing system is taken out by the dyeing and weaving thing, cleans coloring system simultaneously with residual dye in the removal system.
After D, dyeing are finished, obtain the violet sample.
E, the different dyeing condition of control can only obtain the purple of the different depths, are difficult to obtain needed inclined to one side indigo plant or red partially purple, the limitation of traditional one-bath dyeing existence that Here it is.
Embodiment 1～6 is dyed good fabric carries out colour fastness to rubbing and water-fast mensuration of washing COLOR FASTNESS, the results are shown in table 1～2:
Table 1: by the colour fastness to rubbing test result of dyeing and weaving thing
(the Grade A standard is: dry friction COLOR FASTNESS 〉=4 with the Grade A standard of synthetic fiber silk fabrics in the measurement result of COLOR FASTNESS and the national standard (GB/T17253-1998), wet friction COLOR FASTNESS 〉=3, staining COLOR FASTNESS 〉=3, allow wherein two and require low half grade or a low one-level than Grade A) compare as can be known: two bathe the method combination dyeings, the colour fastness to rubbing of fabric and water-fastly wash the Grade A standard that COLOR FASTNESS all can meet synthetic fiber silk fabrics in the national standard.
Claims (5)
1. supercritical CO
2The combination dyeing method of mediation is characterized in that described method comprises: with supercritical CO
2Fluid is a medium, and successively the fabric for the treatment of dyeing with DISPERSE DYES not of the same race dyes, and makes by the dyeing and weaving thing and obtains needed color.
2. the method for claim 1, it is characterized in that method is the dyestuff gradation dyeing that fabric to be dyeed is placed successively different color and lusters respectively, described gradation staining procedure is as follows: will treat that the dyeing and weaving thing places the dyeing system of first kind of dyestuff to carry out the dyeing first time, after dyeing finishes for the first time, the fabric that is colored places the dyeing system of second kind of dyestuff to carry out the dyeing second time again, obtains the fabric of combination dyeing; If necessary, after dyeing finishes for the second time, again fabric is placed the dyeing system of the third dyestuff to dye for the third time, obtain needed color up to fabric;
Described dyeing system is the closed-cycle system that dyeing caldron, dyestuff still and circulating pump are formed; Described first time of dyeing, for the second time or colouring method is as follows for the third time: dyestuff is placed the dyestuff still, treat that the dyeing and weaving thing places dyeing caldron, liquid carbon dioxide is injected dyeing system, under 70～140 ℃, 14～30MPa, the ON cycle pump carries out dyeing cycle to fabric, dyeing time is 30～120min, and the fluid mass flow is 100～120kg/h.
3. method as claimed in claim 2 is characterized in that described first kind, second kind or the third dyestuff are DISPERSE DYES.
4. method as claimed in claim 2 is characterized in that described first kind of dyestuff and second kind of dyestuff are any two kinds in disperse red 343, disperse blue 366, the disperse yellow 241.
5. method as claimed in claim 1 or 2 is characterized in that the described dyeing and weaving thing for the treatment of is a dacron.
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| CN102952416A (en) * | 2012-11-20 | 2013-03-06 | 浙江山川轻纺科技有限公司 | Dye for polyester textures and production process thereof |
| CN103741523B (en) * | 2013-12-30 | 2016-04-20 | 成都纺织高等专科学校 | A kind of supercritical CO 2fluid dispersion dye solubilization colouring method |
| CN105274757B (en) * | 2015-11-09 | 2017-08-08 | 武汉纺织大学 | A kind of single step three primary colors particle flux colouring method |
| WO2018078651A1 (en) * | 2016-10-27 | 2018-05-03 | Ashok Baser Swapneshu | Process for dyeing of textile materials using supercritical fluid |
| CN107904986B (en) * | 2017-12-26 | 2020-11-03 | 中原工学院 | Supercritical CO2Fluid natural textile dye composition and dyeing method |
| CN108867116A (en) * | 2018-04-27 | 2018-11-23 | 青岛即发集团股份有限公司 | A kind of supercritical CO2Colouring method and coloring system |
| CN109235079A (en) * | 2018-08-14 | 2019-01-18 | 青岛即发集团股份有限公司 | A kind of supercritical CO2Cotton and cotton blended fabric colouring method |
| CN111411442A (en) * | 2020-04-01 | 2020-07-14 | 无锡市红博面料馆有限公司 | Roman cloth and manufacturing method thereof |
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