CN111778739A - Acid low-temperature dip dyeing method for chinlon 56 fiber and fabric - Google Patents

Abstract

The invention discloses an acid low-temperature dip dyeing method for nylon 56 fibers and fabrics. The dyeing method comprises the following steps: the acid dye, the neutral dye or the reactive dye is adopted to dye the chinlon 56 fiber or the fabric thereof, and the method (1) has good dyeing effect, deep color and high dye-uptake; (2) the color fastness is good, the friction resistance and the washing resistance can reach more than 4 grades, and the fastness to sunlight can reach more than 6 grades; (3) the process flow is simple, energy is saved, emission is reduced, the dyeing method is a dyeing method for quickly dyeing at low temperature in a short time, the damage to the fiber in the dyeing process is effectively reduced by low-temperature dyeing, the weight loss rate of the fiber is reduced, and the improvement of the finished product yield of the post-process product is facilitated.

Description

Acid low-temperature dip dyeing method for chinlon 56 fiber and fabric

Technical Field

The invention relates to an acid low-temperature dip dyeing method for nylon 56 fibers and fabrics, belonging to the field of textile dyeing and finishing.

Background

Nylon fiber is commonly called nylon (PA for short) and is a general name of thermoplastic resin containing repeated amide groups (-NHCO-) on a molecular main chain. Chinlon, one of the main chemical fiber varieties, appeared in 1935, is the synthetic fiber which realizes industrial production at the earliest time. Although the development of terylene is rapid in recent years, chinlon still competes in synthetic fiber with excellent performances such as strength, wear resistance, elastic recovery rate, moisture absorption and the like, and still occupies an important position for more than half a century. Currently, chinlon 66 and chinlon 6 are most commonly and widely applied, however, most of the synthetic raw materials of the chinlon are derived from derivatives of fossil resources. With the increasing demand of industrial production for nylon materials and the gradual exhaustion of fossil resources, and the increasing concern of people on the problem of environmental protection, the preparation of chemicals by using renewable biomass resources instead of non-renewable fossil raw materials is a main trend of future development.

In the process of manufacturing the traditional chinlon 66, due to the change of processing technology, the molecular weight is higher, hydrogen bonds among molecules are more, the crystallinity and the orientation degree are higher, the amorphous region structure is tighter, the difference among fibers is obviously reflected during dyeing, unevenness is easily generated, and defects such as warp beam and transverse beam are caused. The traditional chinlon is usually dyed by acid dyes under high temperature conditions, and color fixing treatment is needed after dyeing, because most of the dyeing of the chinlon on the acid dyes depends on Van der Waals force and hydrogen bond between dye molecules and fabrics, so that the problems of poor color fastness and the like are caused. The bio-based nylon 56 fiber is a novel bio-based fiber, and no ultralow-temperature high-efficiency dip dyeing method for the nylon 56 fiber exists at present.

Disclosure of Invention

The invention aims to provide an acid bath ultralow temperature high-efficiency dip dyeing method for nylon 56 fibers or fabrics thereof, which adopts acid dye, neutral dye and reactive dye to realize dip dyeing of the nylon 56 fibers or fabrics thereof.

The invention provides an acid bath dip-dyeing method of chinlon 56 fiber or fabric thereof, which comprises the following steps:

dyeing the chinlon 56 fiber or the chinlon 56 fabric by adopting acid dye, neutral dye or reactive dye;

in the acid bath dip dyeing method, the chinlon 56 fiber can be filament or staple fiber;

the content of the terminal amino groups of the chinlon 56 fiber can be 20-80 mol/10⁶gr is preferably 30 to 60mol/10⁶gr, more preferably 45 to 55mol/10⁶gr；

The content of terminal carboxyl groups of the chinlon 56 fiber can be 50-110 mol/10⁶gr, preferably 60 to 90mol/10⁶gr, more preferably 65 to 75mol/10⁶gr。

The crystallinity of the nylon 56 fiber can be 30-70%, preferably 45-65%, and more preferably 45-60%.

The nylon 56 fabric is formed by the nylon 56 fibers, and can be specifically a nylon 56 knitted fabric, a nylon 56 woven fabric or a nylon 56 non-woven fabric.

In the acid bath dip dyeing method, the chinlon 56 fiber can be prepared by a melt direct spinning method or a melt intermittent spinning method;

and adjusting the pH value of the chinlon 56 salt solution to 7.5-8.5, preferably 7.5-8.0.

And adjusting the draft multiple to be 1.1-5 times to realize the adjustment of the crystallinity.

In the acid bath dip dyeing method, the steps of dyeing with the acid dye or the neutral dye are as follows:

preparing the acid dye or the neutral dye into a dye solution, wherein the bath ratio is 1: 2-10, regulating the pH value to 2.0-6.8, adding a dyeing assistant, adding the chinlon 56 fiber or the fabric thereof, dyeing at normal temperature, heating to 30-80 ℃ at the heating rate of 5-10 ℃/min, keeping the temperature for 1-20 min, cooling to room temperature, and carrying out dyeing post-treatment.

In the acid bath dip dyeing method, the steps of dyeing by using the reactive dye are as follows:

preparing the reactive dye into a dye solution, wherein the bath ratio is 1: 2-10 g/L of anhydrous sodium sulphate (added in a liquid preparation process or a constant temperature process) is added, a dyeing auxiliary agent is added, the pH value is regulated to 2.0-6.5, the polyamide 56 fiber or the fabric thereof is added at normal temperature, the temperature is raised to 30-60 ℃, the temperature is kept for 1-20 min, then the temperature is continuously raised to 50-80 ℃, a color fixing agent is added for fixing for 10-30 min, and the temperature is lowered to room temperature for dyeing post-treatment.

The color fixing agent can be a surfactant (cationic), a quaternary ammonium salt without surface activity, a resin type color fixing agent, a cross-linking color fixing agent, a formaldehyde-free color fixing agent and the like, and specifically can be a color fixing agent Y, sodium carbonate or caustic soda.

Specifically, the acid dye may be at least one of azo acid dye, anthraquinone acid dye, triarylmethane acid dye, xanthene acid dye and nitro acid dye;

the acid dye can be acid red NHFS, acid yellow NHFS, acid blue NHFS, F type weakly acidic dye, acid bright red FG, acid yellow G, acid yellow AD, acid red AD, acid gray AD, weakly acidic bright red FG or weakly acidic blue 5R.

Specifically, the neutral dye can be a 1:2 type metal complex dye in an acidic mordant-containing dye, and specifically can be an Annosatel M type metal complex dye and an S type metal complex dye;

the neutral dye may be neutral deep yellow GL, neutral gray 2BL, neutral yellow 2R, neutral soy red B, neutral blue 2R, neutral brown B, neutral gray G, neutral red GAL, neutral Tibetan BR, neutral black AW 200%, neutral yellow TB, neutral yellow R, neutral red 3B, neutral red 10B, neutral red 3G, neutral turquoise blue G, neutral blue R or neutral blue RAWL.

Specifically, the reactive dye can be a chlorotriazine reactive group reactive dye, a vinylsulfone reactive group reactive dye, a multi-reactive group reactive dye, a bromoacrylamide reactive group reactive dye, an epoxy reactive dye or an azide reactive dye;

chloro-s-triazines: a reactive dye K-6G; vinyl sulfones: a reactive dye K-NR; multiple active groups: reactive brilliant red M-3 BE; brominated acrylamides: lanoline blue 3G, reactive red 83, reactive yellow 39, reactive blue 69, annofel red ARC, annofel yellow/golden ARC, annofel blue ARC; reactive dye activity of unknown structure: bright yellow WG, active bright red WG, active brilliant blue WR, active black WG.

Specifically, the dyeing auxiliary can be a pH regulator and a leveling agent;

the pH regulator can be acid, alkali, acidic oxide, basic oxide, weak acid strong base salt, strong acid weak base salt, etc., such as acetic acid, sodium hydroxide, calcium oxide, sodium carbonate, ammonium chloride, etc., such as 1% aqueous solution;

the dosage of the pH regulator can be 0.5-5 g/L;

the leveling agent can be specifically peregal O, a leveling agent JV-905, a leveling agent JV-1, a leveling agent SET, a leveling agent HJ-219 or a leveling agent NL;

the amount of the leveling agent can be 0.1-5% (o.w.f.).

In the acid bath dip dyeing method, after the dyeing step, a post-treatment step is further included;

the post-treatment after dyeing by the acid dye and the neutral dye comprises the following steps: washing with hot water, washing with water and drying in the air;

and (3) hot water washing: washing with hot water at 40-60 ℃ for 1-3 times;

and (3) washing: washing with room temperature water for 1-3 times;

the post-treatment after dyeing by the reactive dye comprises the following steps: hot water washing, soaping, water washing and air drying;

and (3) hot water washing: washing with hot water at 40-60 ℃ for 1-3 times;

and (3) washing: washing with room temperature water for 1-3 times;

the soaping conditions were as follows: 1-5 g/L of soap powder, 40-80 ℃, 5-10 min of time, 1: 15.

the acid bath dyeing method of the chinlon 56 fiber has the advantages that (1) the dyeing effect is good, the color is deep, and the dye-uptake rate is high; (2) the color fastness is good, the color fastness test results of the dyed fabric such as rubbing resistance, washing resistance, sunlight resistance and the like can meet the use requirements, the rubbing resistance and the washing resistance can reach more than 4 grades, and the sunlight resistance color fastness can reach more than 6 grades; (3) the method has the advantages of simple process flow, energy conservation and emission reduction, is a dyeing method for quickly dyeing at low temperature in a short time, effectively reduces the damage to the fiber in the dyeing process by low-temperature dyeing, reduces the weight loss rate of the fiber, and is beneficial to improving the finished product yield of the post-process product.

Drawings

FIG. 1 shows the dyeing effect of polyamide 56 fibers with different terminal amino group contents.

FIG. 2 is a graph showing the dye uptake rate of polyamide fiber dyed with an acid dye (acid blue NHFS) at 70 ℃.

FIG. 3 is a graph showing the dye uptake rate of polyamide fiber dyed with a neutral dye (neutral deep yellow GL) at 65 ℃.

FIG. 4 is a dye-uptake rate curve of polyamide fiber dyed with reactive dye (reactive Brilliant blue D-RV) at 60 ℃.

Detailed Description

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The nylon used in the following examples was 66, a commercially available product, and the amino group content at the test end was 46mol/10⁶gr。

The percentage of dye uptake in the following examples was determined by: and (3) respectively measuring the absorbance of the dye solution before and after dyeing at the maximum absorption wavelength by using a spectrophotometer, and calculating the dyeing percentage according to the following formula: ct ═ 1-A₁/A₀) × 100% (in the formula: A) 100%₀The absorbance of the original dye solution is obtained; a. the₁The absorbance of the residue after dyeing was used. )

The nylon 56 fiber adopted by the embodiment of the invention is prepared by the following method:

preparing a chinlon 56 salt water solution with the concentration of 50 wt% in a salt solution tank, and specifically comprising the following steps: adding 90kg of chinlon 56 dry salt into 55kg of desalted water, completely dissolving, and adjusting the pH value of a salt solution to 7.5-8.5. After preparing salt solution, heating a salt solution tank to 50 ℃, opening a feeding valve to inject the salt solution into a polymerization reaction kettle to start prepolymerization when the temperature reaches a set temperature, wherein the prepolymerization test conditions are as follows: the temperature in the reaction kettle is set to be 212 ℃, the pressure is 1.75MPa, the stirring speed is 60r/min, the reaction is carried out for 2 hours, and then the temperature is raised to be 250 ℃. And (3) when the temperature reaches 250 ℃, reducing the pressure for about 1h, raising the temperature of the reaction kettle to 270 ℃ while reducing the pressure, vacuumizing for about 10min, raising the temperature in the kettle to 275 ℃, completing the polymerization reaction, directly discharging materials, cooling by cold water and air blowing, and cutting by a granulator to obtain the chinlon 56 slices. Drying the slices at 80 ℃ for 22h, and setting spinning conditions as follows: the spinning temperature is 288 ℃, the rotating speed of a metering pump is 16rpm/min, the spinning speed is 1000m/min, the side blowing air pressure is 450pa, the concentration of a winding oiling agent F5103 is 5%, and the drafting multiple and the heating temperature are as follows: the first drawing ratio is 2.5-3.5; the secondary draft ratio is 1.01-1.42; draw box temperature 170; the second pulling temperature is 180 ℃; hotplate temperature 200; the third pulling temperature is 180 ℃. And (4) winding to obtain the nylon 56 fiber.

The pH values of the different salt solutions are shown in Table 1 for different end groups and carboxyl contents of the fibers (the draft control is 3.5).

As can be seen from the data in Table 1, when the pH of the aqueous salt solution is less than 7.5, the terminal group content is low, and when the pH of the aqueous salt solution is greater than 8.5, the acid-amine ratio of the reaction raw material is unbalanced, and polymerization cannot be performed, so that the optimum pH range is 7.5 to 8.0.

TABLE 1 influence of different salt solution pH values on the terminal amino group content of nylon 56 fiber

The method comprises the steps of dyeing a 1# sample and a 3# sample, selecting neutral gray 2BL of a dye, preparing 1% (o.w.f.) dye liquor, enabling the pH value of the dye liquor to be 6.8, adding a leveling agent, and adding 0.5% (o.w.f.) of O, wherein the dyeing bath ratio is 1: 10. Adding the dyed materials (1# and 3#) with different terminal amino group contents at normal temperature; then heating to 70 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 20min to finish dyeing. And cooling the dye liquor to normal temperature, taking out the sample, washing the sample for 1 time at the temperature of 80 ℃, washing the sample for 1 time at the normal temperature by cold water, and air-drying the sample.

The staining effect is shown in FIG. 1, the left panel is sample # 1, and the right panel is sample # 3.

The two samples were tested for dye uptake and were: the staining rate of the sample No. 1 was 68.3%, and the staining rate of the sample No. 3 was 83.6%.

As can be seen from the table 1 and the figure 1, when the pH value is regulated to be 7.5-8.0, the amino-terminated value of the polyamide-56 fiber is high, and the dyeing effect is good.

The different degrees of crystallinity of the fibers corresponding to different draw ratios are shown in table 2 (controlling the pH value of the saline solution of the chinlon 56 to be 7.85).

The obtained nylon 56 fiber was dyed in the above manner, and the dye uptake was as shown in table 2.

TABLE 22 influence of different draft factors on the crystallinity of Nylon 56 fiber

Sample No. 2	Degree of crystallinity (%)	The dye uptake rate%
			① drafting by 2 times	56.8	84.3
② draft 3.4 times	64.0	78.9

As can be seen from the data in table 2, the greater the crystallinity of the fiber, the smaller the amorphous region of the fiber, i.e., the less dye that can enter the interior of the fiber, and the less effective the fiber dyeing.

According to the fiber preparation scheme, the nylon 56 fiber with the salt solution pH of 7.85, the primary drafting of 3.15 times and the secondary drafting of 1.12 times (the co-drafting of 3.53 times) is prepared, and the content of the end amino groups is measured to be 45.2mol/10⁶gr, carboxyl end group content 74.3mol/10⁶gr and a crystallinity of 65.2%, and the following dyeing treatment was performed.

Example 1 measurement of dye uptake Rate curves of Chinlon 56 and Chinlon 66 dyed with acid dyes

Preparing 1g/L acid blue NHFS dye standard dye solution, preparing 10 groups of dye baths with 2mL standard dye solution, wherein the fiber is 0.2g, the bath ratio is 1:500, adjusting the pH value of the obtained dye solution to 4.67, simultaneously putting the dye baths into a dyeing machine with the dyeing temperature set to 70 ℃, respectively dyeing for 5min, 10min, 15min, 20min, 30min, 45min, 60min, 75min, 90min and 120min, taking out samples, washing the samples with water at normal temperature, drying the samples, and stripping the samples to test the dyeing rate curve of the samples.

The dyeing rate curves of chinlon 56 and chinlon 66 dyed by the acid dye are shown in figure 2. The balanced dye uptake percentage of nylon 56 and nylon 66 is shown in table 3.

Example 2 determination of the dye uptake rates of Chinlon 56 and Chinlon 66 dyed with neutral dyes

Preparing 1g/L neutral deep yellow GL dye standard dye solution, adjusting the pH value of the obtained dye solution to 6.8, the dyeing temperature to 65 ℃, and the rest dyeing process is the same as the acid dye dyeing rate method in the example 1.

The dyeing rate curves of chinlon 56 and chinlon 66 dyed by neutral dyes are shown in figure 3. The balanced dye uptake percentage of nylon 56 and nylon 66 is shown in table 3.

Example 3 determination of percentage of Chinlon 56 and Chinlon 66 dyed with reactive dyes

Preparing 1g/L of reactive brilliant blue D-RV dye standard dye solution, adding 5g/L of anhydrous sodium sulphate into the dye solution, adjusting the pH value of the obtained dye solution to 3.0, and dyeing at 60 ℃ (no color fixing step), wherein the rest dyeing processes are the same as the acid dye dyeing rate method in the example 1.

The dyeing rate curves of chinlon 56 and chinlon 66 dyed by reactive dyes are shown in figure 4. The balanced dye uptake percentage of nylon 56 and nylon 66 is shown in table 3.

TABLE 3 dye uptake percentage of acid dyes, neutral dyes, reactive dyes for dyeing nylon 56 and nylon 66

The dye uptake percentage curve of chinlon 56 and chinlon 66 dyed by the acid dye, the neutral dye and the reactive dye in the examples 1-3 can be known as follows: the different types of dyes respectively dye the nylon 56 and the nylon 66 fibers under the low temperature condition, the nylon 56 fibers can basically reach the balanced dye-uptake percentage within 20min of dyeing, the nylon 66 can reach higher dye-uptake percentage at least within 60min, and the balanced dye-uptake percentage of the nylon 56 is obviously higher than that of the nylon 66.

Example 4 acid dye Dip-dyeing of Nylon 56 fiber

Selecting a dye of acid blue NHFS, preparing a 2% (o.w.f.) dye solution, wherein the pH value of the dye solution is 4.67, adding a leveling agent, and adding 0.5% (o.w.f.) of O flatly, wherein the dyeing bath ratio is 1: 5. Adding 2g of dyed fabric at normal temperature; then heating to 70 ℃ at the heating rate of 5.5 ℃/min, preserving heat for 15min, completing dyeing, cooling the dye liquor to room temperature, taking out the sample, washing with hot water at 70 ℃ for 3 times, washing with water at room temperature for 1 time, and drying in the air.

Comparative example 1: chinlon 66 was dyed as described above and the results of the two fiber tests are shown in Table 4.

Example 5 neutral dye Dip-dyeing of Nylon 56 fiber

Selecting neutral deep yellow GL of a dye to prepare 3% (o.w.f.) dye liquor, wherein the pH value of the dye liquor is 6.8, and adding 1.5% (o.w.f.) leveling agent HJ-219, wherein the dyeing bath ratio is 1: 10. Adding 2g of dyed fabric at normal temperature; then heating to 65 ℃ at the heating rate of 5 ℃/min, preserving heat for 20min, completing dyeing, cooling the dye liquor to room temperature, taking out the sample, washing with hot water at 60 ℃ for 1 time, washing with water at room temperature for 1 time, and drying in the air.

Comparative example 2: chinlon 66 was dyed as described above and the results of the two fiber tests are shown in Table 4.

Example 6 reactive dye Dip-dyeing of Nylon 56 fiber

Selecting dye reactive brilliant blue D-RV, preparing 3% (o.w.f.) dye liquor, wherein the pH value of the dye liquor is 3.0, the dyeing bath ratio is 1:8, and adding 2% (o.w.f.) leveling agent JV-1 and anhydrous sodium sulphate 5 g/L. Adding 2g of a fabric to be dyed under the condition of normal temperature, heating a dyeing solution to 40 ℃ at the speed of 1 ℃/min, dip-dyeing for 15min, then continuously heating to 60 ℃ at the speed of 1 ℃/min, adding 20g/L of sodium carbonate, fixing color and preserving heat for 20min, finishing dyeing, cooling the dyeing solution to room temperature, taking out a sample, washing the sample with hot water at the temperature of 40 ℃ for 1 time, washing the sample with water at the room temperature for 1 time, soaping (2g/L of soap chips, 45 ℃, 10min, the bath ratio of 1:10), washing with room-temperature water for 1 time, and drying.

Comparative example 3, nylon 66 was dyed according to the above method, and the results of the two fiber tests are shown in table 4.

TABLE 4 color fastness test results of chinlon 56 and 66 dyed with acid dye, neutral dye and reactive dye

As can be seen from the dyeing effects of the examples 4-6 and the comparative examples 1-3, the similar dyes respectively dye the chinlon 56 and the chinlon 66 under the same low temperature condition, the apparent depth of the chinlon 56 is obviously higher than that of the chinlon 66, the color fastness of the chinlon 56 is better than that of the chinlon 66, and the requirements of market application are met.

Claims (10)

1. An acid bath dip-dyeing method of chinlon 56 fiber or fabric thereof comprises the following steps:

dyeing the chinlon 56 fiber or the chinlon 56 fabric by adopting acid dye, neutral dye or reactive dye;

the content of terminal amino groups of the chinlon 56 fiber is 20mol/10⁶gr～80mol/10⁶gr, carboxyl end group content 50mol/10⁶gr～110mol/10⁶gr, a crystallinity of 30 to 70%.

2. The acid bath exhaust dyeing method according to claim 1, characterized in that: the nylon 56 fiber is prepared by a melt direct spinning method or a melt intermittent spinning method;

adjusting the pH value of the chinlon 56 salt solution to 7.5-8.5;

and adjusting the draft multiple to be 1.1-5 times.

3. The acid bath exhaust dyeing method according to claim 1 or 2, characterized in that: the steps of dyeing with the acid dye or the neutral dye are as follows:

preparing the acid dye or the neutral dye into a dye solution, wherein the bath ratio is 1: 2-10, adding a dyeing assistant, regulating the pH value to 2.0-6.8, adding the chinlon 56 fiber or the fabric thereof, dyeing at normal temperature, heating to 30-80 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 1-20 min, cooling to room temperature, and carrying out dyeing post-treatment.

4. The acid bath exhaust dyeing method according to claim 1 or 2, characterized in that: the steps of dyeing with the reactive dye are as follows:

preparing the reactive dye into a dye solution, wherein the bath ratio is 1: 2-10 g/L of anhydrous sodium sulphate is added, a dyeing auxiliary agent is added, the pH value is regulated to 2.0-6.5, the polyamide 56 fiber or the fabric thereof is added at normal temperature, the temperature is raised to 30-60 ℃, dip dyeing is carried out for 1-20 min, then the temperature is raised to 50-80 ℃, a color fixing agent is added for fixing color for 10-30 min, and the temperature is lowered to room temperature for post-treatment.

5. The acid bath exhaust dyeing method according to any one of claims 1 to 4, characterized in that: the acid dye is any one of azo acid dye, anthraquinone acid dye, triarylmethane acid dye, xanthene acid dye and nitro acid dye.

6. The acid bath exhaust dyeing method according to any one of claims 1 to 4, characterized in that: the neutral dye is a 1:2 type metal complex dye in an acidic mordant-containing dye.

7. The acid bath exhaust dyeing method according to any one of claims 1 to 4, characterized in that: the reactive dye is a chloro-s-triazine reactive group reactive dye, a vinyl sulfone reactive group reactive dye, a multi-reactive group reactive dye, a bromo-acrylamide reactive group reactive dye, an epoxy reactive dye or an azide reactive dye.

8. The acid bath exhaust dyeing method according to any one of claims 3 to 7, characterized in that: the dyeing auxiliary agent is a pH regulator and a leveling agent.

9. The acid bath exhaust dyeing method according to claim 8, characterized in that: the pH regulator is acid, alkali, acid oxide, alkaline oxide, weak acid strong base salt or strong acid weak base;

the leveling agent is peregal O, a leveling agent JV-905, a leveling agent JV-1, a leveling agent SET, a leveling agent HJ-219 or a leveling agent NL.

10. The acid bath exhaust dyeing method according to any one of claims 1 to 9, characterized in that: the nylon 56 fiber filament or staple fiber;

the nylon 56 fabric is a nylon 56 knitted fabric, a nylon 56 woven fabric or a nylon 56 non-woven fabric.

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