CN103074766B - Cellulosic fiber fabric reactive dye salt-free deep-color dyeing method - Google Patents

Abstract

The invention relates to a cellulosic fiber fabric reactive dye salt-free deep-color dyeing method, which comprises the following steps: (1) preparing a modifier aqueous solution, increasing the temperature to 60-80 DEG C, adding a test sample, stirring, adding sodium hydroxide, stirring, washing and drying to obtain a modifier test sample; and (2) adding a reactive dye and a levelling agent, increasing the temperature to 60-80 DEG C, adding the modifier test sample, dyeing for 20-30 minutes in a stirring manner, adding substitution alkali, dyeing for 30-45 minutes in a stirring and thermal insulation manner, decreasing the temperature to the room temperature, soaping, washing and oven drying. According to the invention, the modifier is used for modifying cellulosic fibers, so that the repulsive force between dye anions and fibers can be reduced, the purpose of fabric reactive dye salt-free dyeing can be achieved, the method is simple and convenient to operate, the effect is obvious, no additional equipment is required, and the cost is controllable.

Description

A kind of cellulose base fiber fabric reactive dye salt-free deep color dyeing method

Technical field

The invention belongs to cellulose dyeing method field, particularly a kind of cellulose base fiber fabric reactive dye salt-free colouring method.

Background technology

China's textile industry year water consumption is more than 10,000,000,000 tons, and wastewater discharge accounts for the 6th of national every profession and trade.Wherein dyeing is again the discharge of wastewater rich and influential family in textile industry, every day the discharge of wastewater of nearly 4,000,000 tons, government need spend a large amount of funds to carry out sewage disposal every year.Promoting energy-saving and emission-reduction policy is the inevitable choice of building a resource-conserving and environment-friendly society.The composition of dyeing waste water has notable difference according to the difference of production process, and wherein reactive dyed wastewater mainly contains two and originates greatly, and one is the utilization rate that hydrolysis of reactive dye reaction reduces dyestuff, and dyestuff more in dyeing after washing liquid, causes the pollution of water resource.On the other hand, adding of a large amount of inorganic salts of dyeing course, do not processed by simple physical chemistry and biochemical method.In the middle of Industrial Waste Water Treatments, the intractability of brine waste will far away higher than the dyestuff of hydrolysis, and for this reason, recent domestic with regard to how reducing the consumption of salt in Dyeing with Reactive Dyes is studied, and less salt even salt-free dyeing has become an important issue.

REACTIVE DYES be can with the dye of processbearing astrocyte covalent bonds, its molecular structure is simple, bright in colour, and chromatogram is comparatively complete, because of its preferably cost performance be widely used at dyeing.But one of its subject matter is dyestuff to be utilized low, needs to add a large amount of electrolyte in dyeing course, particularly more outstanding during large bath ratio dyeing.By dyeing basic theories, when reactive dyestuffs in exhaustion, salt mainly plays electron screening effect.Cellulose fibre is surface band negative electrical charge in alkaline aqueous solution, if in absorption after REACTIVE DYES anion, the negative electrical charge of dye ions can make the more negative electrical charge of fiber band, this negative electrical charge can stop on REACTIVE DYES anion and contaminates, reduce dyeing rate and the upper dye amount of balance, reduce dye utilization rate and deep-cutting gorge.During dyeing, in dye liquor, add electrolyte, it plays cationization effect, namely plays electron screening effect, reduces the repulsion of dye anion and fiber negative electrical charge, and then plays short dye effect.But the sodium ion of inorganic salts (as sodium sulphate) dissociation in dye liquor, on the one hand because its hydratability is strong, in dye liquor, its surface can form one deck hydrated sheath, thus causes it can greatly reduce in the electric double layer effect on conpressed fibers surface; On the other hand, sodium ion molecular weight, and Van der Waals force between fiber is lower, thus not easily near fiber surface, namely enable close, also can leave fiber surface along with the flowing of dye liquor, therefore need to add a large amount of electrolyte when dyeing and urge to contaminate.From above-mentioned analysis, the salt-free or low salt dyeing of REACTIVE DYES can carry out from following several aspect:

(1) low-salt reactive dyes exploitation

From dyestuff chemistry structure, depend primarily on structure and the ratio of the hydrophobic of dyestuff and hydrophilic radical, especially with number and the position of anion base in molecule (sulfonic group).Anion base is the more, just large with the electrical repulsion of fiber, reduces substantivity more remarkable, otherwise the more, aromatic ring planar alignment is stronger for hydrophobic grouping, and dyestuff is direct just higher, and salt consumption is lower.Reached the object of low salt dyeing by the structure rationally changing dyestuff, but this method to there is production cost too high, fundamentally can not realize salt-free dyeing.Zhang Hua, Zhao Tao. a kind of synthesis of quaternary ammonium salt cationic REACTIVE DYES and the dyeability research [J] 2009,4 (46), 32 ~ 35 to cotton fiber.Be dye matrix with 1-amino anthraquinones, first react with Cyanuric Chloride, rear introducing tertiary amine, has finally synthesized a kind of active cationic dye by quaternised for tertiary amine method again.Adopt this kind of REACTIVE DYES to carry out salt-free dyeing to COTTON FABRIC and can obtain higher dye-uptake and degree of fixation.

(2) rational dyeing

Appropriate design and control dyeing, if reduction dyeing temperature and short liquor dyeing are also the important means realizing low salt dyeing.From dyeing theory, dyeing temperature is lower and bath raio is less, and the substantivity of dyestuff is higher, and salt consumption can greatly reduce.By strictly accurately controlling dyeing course, adopting advanced dyeing to produce, the consumption of salt dye material can be reduced, and production efficiency is high, the percentage of A-class goods is high, with short production cycle, production cost is low, contaminated wastewater is few.But short liquor dyeing, first require dissolubility and the good stability of dyestuff, another difficult point is level-dyeing property, requires very high to device structure and control system.And low temperature dyeing, suitable auxiliary agent must be selected to improve dissolving or the dispersiveness of dyestuff, accelerate upper dye and the fixation speed of dyestuff, also there is dyeing time long, the uppity shortcoming of reappearance.

(3) multi-functional generation salt agent and salt-free dyeing auxiliary

Add in dye liquor for salt agent, make itself and dyestuff form loose combination and reduce the electrical of dyestuff; Or first by fibers adsorption, reduce fiber interface electrical, reduce electrostatic repulsion between fiber and dyestuff, improve its dye-uptake and degree of fixation, realize low salt dyeing.Liu Lijun, Yao Jinbo. betaine in REACTIVE DYES to application [J] .2009 in COTTON FABRIC low salt dyeing, 4 (28), 53 ~ 57. betaines are a kind of nontoxic labile amphoteric compounds, with a positive charge and a negative electrical charge in its molecule, add betaine in dye liquor after, cation in betaine molecule and dye anion are split into ionic bond and are combined, because sulfonic dissociative is larger than carboxyl, after betaine cation and sulfonic group anion binding, the negative electricity of REACTIVE DYES will be reduced, thus the Coulomb repulsion reduced between dyestuff and fiber, dyestuff is strengthened the substantivity of fiber, thus reach low salt dyeing.After adding betaine, with active red B-3BF to cotton fabric dyeing process, can reduce the consumption of about 60% salt, dyefastness also increases.

(4) cellulose fiber cation modification

Cationization of pulp fiber modification mainly makes cationic compound (mainly nitrogen-containing compound) anchor on fiber by chemical bond or physical absorption.Fiber, after chemical modification, can improve affinity between dyestuff and fiber greatly, thus improves degree of exhaustion and the degree of fixation of dyestuff, thus reaches less salt or salt-free dyeing.In recent years, correlative study is attempted to give fiber other functions while cotton fiber cationization, as antibiotic property, anti-crease property etc., development of new environment friendly biological matter cationic reagent simultaneously, as shitosan class, starch derivatives class reagent etc., also become the trend of cationization of pulp fiber reagent development in recent years gradually.

Li Baomei, Zhao Yaqin. cotton fiber cation modifying technical study. dyeing and finishing technique [J] .2011,10 (33), 18 ~ 31. adopt modifier 3 chlorine-2-hydroxyl propyl group tri alkyl ammomium chloride to carry out chemical modification to COTTON FABRIC, modified COTTON FABRIC is positively charged, and the repulsion between dyestuff reduces, reach the object of salt-free dyeing.

In recent years, under the pulling that textile industry increases steadily fast, dyeing is developed rapidly, and meanwhile, is also more and more subject to the restriction of resource, environment.It is low to there is dye utilization rate in reactive dyeing, salt dosage is large, modifying porcelain burden heavily waits series of problems, therefore REACTIVE DYES less salt or salt-free dyeing technique is advanced to become the current inexorable trend adapting to environmental requirement, also be the inevitable choice of building a resource-conserving and environment-friendly society simultaneously, implement a scientific outlook on development, realize industry value chain, change the inevitable approach of industrial economy growth pattern.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of cellulose base fiber fabric reactive dye salt-free colouring method, the method uses modifier to carry out modification to cellulose fibre, dye anion and interfibrous repulsion can be reduced, reach the object of reactive dye salt-free dyeing, the method is easy and simple to handle, successful, without the need to increasing equipment, cost can control.

(1) method of modifying

Formula:

Modifier concentration: 20 ~ 50g/L

NaOH: 5 ~ 25g/L

Bath raio: 1:8 ~ 30

Step

Preparation modifier aqueous solution is warming up to 60 ~ 80 DEG C, adds cellulose base fiber fabric, stirs 5 ~ 15min and adds NaOH, stir 15 ~ 30min, washing, dry.

(2) colouring method

Formula:

REACTIVE DYES 2 ~ 5% (owf)

Leveling agent o-250.2 ~ 1g/L (owf)

Substitute alkali 1 ~ 3% (owf)

Bath raio 1:8 ~ 30

Step

Preparation dye liquor (adding dyestuff, levelling agent) is warming up to 60 DEG C, adds modified cellulose fibre fabric, stirs dyeing 20 ~ 30min and adds substitute alkali, stirs insulation dyeing 30 ~ 45min and is cooled to room temperature with 2 ~ 5 DEG C/min, soaps, washes, dries.

To soap prescription

Neutral soap flakes 2g/L, soda ash 2g/L, temperature of soaping 95 DEG C, soap time 10min, bath raio 1:20.

Modifier in described step (1) is cation modifier, and general formula is r ₁, R ₂, R ₃for lower alkyl, lower alkyl is CH ₃or C ₂h ₅.

Levelling agent in described step (2) is leveling agent o-25, fatty alcohol and ethylene oxide condensate, and Haian County and occasion Chemical Co., Ltd. provide.

(3) performance test

A. REACTIVE DYES dye-uptake measures.

Empirically a dye bath prepared by dyestuff by prescription respectively, be placed in same water bath with thermostatic control, add in one of them dye bath by dyeing and weaving thing, do not add in another dye bath and claimed standard dye liquor by dyeing and weaving thing, so the intensification of dyeing curve or insulation are pressed in latter two dye bath, add glauber salt (if the fabric after cation-modified does not then add) and soda ash, until it is complete to dye.By dyeing residual liquid distilled water diluting to 500ml, draw 20ml and join in 100ml volumetric flask, with distilled water diluting to 100ml, with the maximum absorption wavelength λ of spectrophotometric determination dyestuff _max, at λ _maxplace measures the absorbance B of dyeing residual liquid; The standard dye liquor of experience dyeing course is also diluted to 500ml, draws in 5ml to 100ml volumetric flask, with distilled water diluting to 100ml, in the absorbance A of maximum absorption wave strong point bioassay standard dye liquor, be then calculated as follows the dye-uptake E(% of dyestuff):

$E=100\%-\frac{B}{A\×n}\×100\%$

In formula: n is the multiple of the test concentrations of standard dye liquor and dyeing residual liquid.

Note: standard dye liquor draws 5ml after being diluted to 500ml, with distilled water diluting to 100ml, dyeing residual liquid draws 20ml after being diluted to 500ml, with distilled water diluting to 100ml, then n=20/5=4.

B. reactive dye color fixing rate measures.

Fabric dye finishes after washing, soap boiling (soap flakes 2g/L, soda ash 2g/L, 95 DEG C, 10min, bath raio 1:20), dries.Equally, prepare two parts of soap boiling liquid respectively, a for DYED FABRICS soap boiling, another part is used as reference standard soap lye.Standard soap lye is diluted to 500ml, draws in 5ml to 100ml volumetric flask, with distilled water diluting to 100ml, at λ _maxplace measures its absorbance C; Separately the cleaning solution of DYED FABRICS is mixed with soap boiling raffinate, after distilled water diluting to 500ml, draw in 20ml to 100ml volumetric flask, with distilled water diluting to 100ml, at λ _maxplace measures the absorbance D of this mixed liquor, then following formula is calculated degree of fixation F(%):

$F=E-\frac{D}{C\×n}\×100\%$

In formula: n is the multiple of the test concentrations of standard soap lye and dyeing residual liquid.

The mensuration of c.K/S value.Sample is built up four layers of position that test five is different on SF600 type Computer color testing color matching instrument, when the error of each reading is less than 0.1, write down the K/S value of every block sample;

D. sunlight fastness.With reference to GB/T8427-1998 " textile color stability tests resistance to artificial light COLOR FASTNESS: xenon arc ";

E. colour fastness to rubbing.With reference to GB/T3920-1997 " textile color stability test colour fastness to rubbing ".

The general formula of the cation modifier that the present invention is used is:

Wherein: R ₁, R ₂, R ₃for lower alkyl, as CH ₃, C ₂h ₅deng.

beneficial effect

(1) the present invention uses this modifier to carry out modification to cellulose fibre, can reduce dye anion and interfibrous repulsion, reaches the object of reactive dye salt-free dyeing;

(2) the present invention is easy and simple to handle, successful, and without the need to increasing equipment, cost can control.

Detailed description of the invention

Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.

Embodiment 1

Preparation modification liquid (bath raio 1:10, cation modifier 30g/L), is warming up to 60 DEG C, adds COTTON FABRIC, stirs 5 ~ 15min, adds alkaline agent 15g/L, stirs 15 ~ 30min, and washing is dried.

Preparation dye liquor (the yellow 0.44%owf of the black 3.7%owf of bath raio 1:10, ED-Q, the plain 3RS of China of section, the red 0.19%owf of the section plain 3BSN of China), leveling agent o-250.5g/L, is warming up to 60 DEG C, adds modified COTTON FABRIC, stir dyeing 20 ~ 30min, add substitute alkali 2g/L, stir insulation dyeing 30 ~ 45min, be cooled to room temperature with 2 ~ 5 DEG C/min, soap (neutral soap flakes 2g/L, soda ash 2g/L, 95 DEG C, 10min, bath raio 1:20), washing, dries, test performance (the results are shown in Table 1).

Table 1

Embodiment 2

Preparation modification liquid (bath raio 1:10, cation modifier 45g/L), is warming up to 60 DEG C, adds COTTON FABRIC, stirs 5 ~ 15min, adds alkaline agent 15g/L, stirs 15 ~ 30min, and washing is dried.

Preparation dye liquor (the yellow 0.44%owf of the black 3.7%owf of bath raio 1:10, ED-Q, the plain 3RS of China of section, the red 0.19%owf of the section plain 3BSN of China), leveling agent o-250.2g/L, is warming up to 60 DEG C, adds modified cotton fabric, stir dyeing 20 ~ 30min, add substitute alkali 2g/L, stir insulation dyeing 30 ~ 45min, be cooled to room temperature with 2 ~ 5 DEG C/min, soap (neutral soap flakes 2g/L, soda ash 2g/L, 95 DEG C, 10min, bath raio 1:20), washing, dries, test performance (the results are shown in Table 2).

Table 2

Embodiment 3

Preparation modification liquid (bath raio 1:10, cation modifier 15g/L), is warming up to 60 DEG C, adds Modal fibre fabric, stirs 5 ~ 15min, adds alkaline agent 15g/L, stirs 15 ~ 30min, and washing is dried.

Preparation dye liquor (the yellow 0.44%owf of the black 3.7%owf of bath raio 1:10, ED-Q, the plain 3RS of China of section, the red 0.19%owf of the section plain 3BSN of China), leveling agent o-251g/L, is warming up to 60 DEG C, adds modification Modal fibre fabric, stir dyeing 20 ~ 30min, add substitute alkali 2g/L, stir insulation dyeing 30 ~ 45min, be cooled to room temperature with 2 ~ 5 DEG C/min, soap (neutral soap flakes 2g/L, soda ash 2g/L, 95 DEG C, 10min, bath raio 1:20), washing, dries, test performance (the results are shown in Table 3).

Table 3

Embodiment 4

Preparation modification liquid (bath raio 1:10, cation modifier 25g/L), is warming up to 60 DEG C, adds Modal fibre fabric, stirs 5 ~ 15min, adds alkaline agent 10g/L, stirs 15 ~ 30min, and washing is dried.

Preparation dye liquor (the yellow 0.44%owf of the black 3.7%owf of bath raio 1:10, ED-Q, the plain 3RS of China of section, the red 0.19%owf of the section plain 3BSN of China), leveling agent o-250.2g/L, is warming up to 60 DEG C, adds modification Modal fibre fabric, stir dyeing 20 ~ 30min, add substitute alkali 2g/L, stir insulation dyeing 30 ~ 45min, be cooled to room temperature with 2 ~ 5 DEG C/min, soap (neutral soap flakes 2g/L, soda ash 2g/L, 95 DEG C, 10min, bath raio 1:20), washing, dries, test performance (the results are shown in Table 4).

Table 4

Claims (1)

1. a cellulose base fiber fabric reactive dye salt-free deep color dyeing method, comprising:

(1) modification liquid: bath raio 1:10, cation modifier 45g/L is prepared; Be warming up to 60 DEG C, add COTTON FABRIC, stir 5 ~ 15min, add alkaline agent 15g/L, stir 15 ~ 30min, washing, dry;

(2) dye liquor is prepared: the black 3.7%owf of bath raio 1:10, ED-Q, the red 0.19%owf of the yellow 0.44%owf of the plain 3RS of China of section, the section plain 3BSN of China; Leveling agent o-25 0.2g/L, is warming up to 60 DEG C, adds modified cotton fabric, stirs dyeing 20 ~ 30min, add substitute alkali 2g/L, stir insulation dyeing 30 ~ 45min, be cooled to room temperature with 2 ~ 5 DEG C/min, soap: neutral soap flakes 2g/L, soda ash 2g/L, 95 DEG C, 10min, bath raio 1:20; Washing, dries; Wherein, modifier is cation modifier, and general formula is r ₁, R ₂, R ₃for CH ₃or C ₂h ₅.