CN111778735A

CN111778735A - Acid rapid pad dyeing method for chinlon 56 fiber and fabric thereof

Info

Publication number: CN111778735A
Application number: CN202010002512.7A
Authority: CN
Inventors: 郝新敏; 郭亚飞; 梁高勇; 夏鹏泽; 闫金龙; 乔荣荣
Original assignee: Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
Current assignee: Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
Priority date: 2020-01-02
Filing date: 2020-01-02
Publication date: 2020-10-16

Abstract

The invention discloses an acid rapid pad dyeing method for chinlon 56 fiber and fabric thereof. The acid bath pad dyeing method of the chinlon 56 fiber or the fabric thereof comprises the following steps: pad dyeing is carried out on 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，The crystallinity is 30 to 70%. The dyeing method has the advantages that (1) the dyeing effect is good, and the color is dark; (2) the color fastness is good, the friction resistance, the washing resistance, the chlorine bleaching resistance, the seawater resistance, the perspiration resistance, the soaping resistance and the like of the dyed fabric can reach more than 3-4 grades, the sunlight color fastness can reach more than 6 grades, and the use requirement is met. (3) The method has simple process flow, energy conservation and emission reduction; (4) the raw materials can adopt bio-based chinlon 56 fiber to meet the requirements of environmental protection and are environment-friendly.

Description

Acid rapid pad dyeing method for chinlon 56 fiber and fabric thereof

Technical Field

The invention relates to an acid rapid pad dyeing method for chinlon 56 fiber and fabric thereof, 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 traditional chinlon 66 fiber manufacturing process, due to the change of processing technology, the content of terminal amino groups in a fiber microstructure is low, the saturation value is low, the molecular weight of the chinlon 66 is high, the number of intermolecular hydrogen bonds is large, the crystallinity and the orientation degree are high, the amorphous region structure is compact, the content of amino groups in the fiber is low, the difference between the fibers is obviously reflected during dyeing, and unevenness is easily generated to cause defects such as 'warp willow' and 'crosspiece'. The traditional chinlon is usually dyed by acid dye, and color fixing treatment is needed after dyeing, because the amino value at the tail end of the chinlon is small, most of chinlon dyed by the acid dye is combined by Van der Waals force and hydrogen bonds 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 low-temperature rapid pad dyeing method for the nylon 56 fiber exists at present.

Disclosure of Invention

The invention aims to provide an acid rapid pad dyeing method for chinlon 56 fibers and fabrics thereof, which adopts acid dye, neutral dye and reactive dye to realize pad dyeing of the chinlon 56 fibers or the fabrics thereof.

The nylon 56 fiber can be filament or staple fiber, and the nylon 56 fabric can be nylon 56 knitted fabric, nylon 56 woven fabric or nylon 56 non-woven fabric.

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

pad dyeing is carried out on 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, preferably 20 to 60mol/10⁶gr, more preferably 45 to 55mol/10⁶gr；

The content of terminal carboxyl groups of the chinlon 56 fiber is 50mol/10⁶gr～110mol/10⁶gr, preferably 60 to 90mol/10⁶gr, more preferably 65 to 75mol/10⁶gr；

The crystallinity of the nylon 56 fiber is 30-70%, preferably 45-65%, and more preferably 50-65%.

In the acid bath pad dyeing method, the chinlon 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, preferably 7.5-8.0;

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

The padding liquid comprises dye and dyeing auxiliary agent;

the padding liquid also comprises a solvent, and the solvent can be water.

The dye in the invention is selected from any one of the following: acid dyes, neutral dyes and reactive dyes.

In the acid bath pad dyeing method, the steps of dyeing by using the acid dye or the neutral dye are as follows: soaking the dyed object in padding liquor containing dye and dyeing auxiliary agent, padding by padder, controlling padding rate range, steaming or baking, and finally carrying out dyeing post-treatment;

the dye is the acid dye or the neutral dye.

The padding liquor can be at room temperature;

because the dye uptake rates of different dyes are different, the soaking time can be 1-10 min;

the pH value of the padding liquor can be 2.5-6.8, and specifically can be 3.0-6.8;

adopting a mode of one-dipping one-rolling, two-dipping two-rolling or multi-dipping multi-rolling;

in the padding liquor, the concentration of the dye can be 5 g/L-40 g/L, and specifically can be 10 g/L-30 g/L;

the concentration of the dyeing auxiliary agent can be 1 g/L-60 g/L, and specifically can be 15 g/L-30 g/L.

In the padder, the padder speed is controlled to be 35-45 m/min, and the rolling pressure is controlled to be 0.18-0.25 MPa;

the predetermined rolling reduction may be 50 to 80%, and further 65 to 75%.

The temperature of the steaming or baking is: 50-100 ℃, and further 70-90 ℃; the time period may be 1 to 30min, and further 10 to 30 min.

The post-dyeing treatment comprises: washing with hot water, washing with water, and air drying.

Hot water washing: washing with hot water at 50-80 ℃ for 1-3 times;

washing with water: washing with water at room temperature for 1-3 times.

In the acid bath pad dyeing method, the reactive dye can be used for dyeing according to the following 1) or 2):

1) soaking the dyed object in padding liquor containing dye, auxiliary agent and color fixing agent, controlling the padding rate range by padder, steaming or baking, and finally carrying out dyeing post-treatment;

2) soaking the dyed object in padding liquor containing dye and auxiliary agent, padding the object by a padder, controlling the padding rate range, padding the object with fixing liquor, steaming or baking, and finally performing dyeing post-treatment;

the dye is the reactive dye.

Wherein the padding liquor can be at room temperature;

the pH value of the padding liquor can be 2.5-7, and specifically can be 2.5-6.8;

The concentration of the color fixing agent can be 5-70 g/L, specifically 20-30 g/L, and the color fixing agent is soaked for 1-10 min.

The color fixing agent can be a surfactant (cationic type), 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 can be specifically sodium carbonate and sodium bicarbonate.

The padding retention rate of the fabric in the padding color fixing solution can be 50-80%, and further can be 70-80%.

the specified rolling reduction may be: 50 to 80%, and further 70 to 80%.

The baking or steaming temperature: 50-100 ℃, and further 70-90 ℃; the time period may be 1 to 30min, and further 10 to 30 min.

The post-dyeing treatment comprises: hot water washing, soaping, water washing and air drying.

Hot water washing: washing with hot water at 50-80 ℃ for 1-3 times;

washing with water: washing with water at room temperature for 1-3 times.

The soaping conditions are as follows: 1 g/L-5 g/L standard soap chips, bath ratio: 1: soaping for 1-10 min at 50-80 ℃ for 5-15;

the acid dye can be azo acid dye, anthraquinone acid dye, triarylmethane acid dye, xanthene acid dye, nitro acid dye, etc.

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.

The neutral dye is 1:2 type metal complex dye in acid mordant-containing dye, and specifically can be Annoset M type metal complex dye or 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.

The reactive dye can be 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;

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 and active black WG;

the dyeing auxiliary agent can be a pH regulator, a leveling agent and/or a penetrating 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 leveling agent CAN be specifically peregal O, a leveling agent CAN, an acidic leveling agent JV-905 or a leveling agent GZ255 YNL;

the penetrant may specifically be the penetrant JFC.

The acid bath pad dyeing method of the chinlon 56 fiber has the advantages that (1) the dyeing effect is good, and the color is dark; (2) the color fastness is good, the friction resistance, the washing resistance, the chlorine bleaching resistance, the seawater resistance, the perspiration resistance, the soaping resistance and the like of the dyed fabric can reach more than 3-4 grades, the sunlight color fastness can reach more than 6 grades, and the use requirement is met. (3) The method has simple process flow, saves energy and reduces emission, and is a dyeing method for rapid dyeing at low temperature in short time; (4) the raw material adopts bio-based chinlon 56 fiber to meet the requirement of environmental protection and is environment-friendly.

Drawings

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

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 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 PA56 draft multiple 2	56.8	84.3
② PA56 draft factor 3.4	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.

The percentage dye uptake described in the following examples was determined as follows: 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. )

Example 1 pad dyeing of Nylon 56 Fabric with acid blue NHFS dye

The adopted dyed fabric is nylon 56 fabric with the specification of 10cm multiplied by 10 cm.

The padding liquor comprises the following components: preparing 100mL of dye solution which comprises an acid dye (acid blue NHFS), a dyeing auxiliary (a dye-blocking agent RF) and a solvent (water); wherein the concentration of the acid dye is 30g/L, and the concentration of the dyeing auxiliary agent is 25 g/L; the pH of the padding liquor was 4.7.

And (3) finishing the configuration of the padding liquid, soaking the blended fabric in the padding liquid for 3min by adopting a one-dip one-pad mode at room temperature, controlling the padder speed to be 40m/min, the pad pressure to be 0.2MPa, the padding rate to be about 75 percent, baking the padded fabric for 15min at the temperature of 100 ℃, taking out a sample, washing the sample once in hot water at the temperature of 70 ℃, washing once at normal temperature, and air-drying to finish the padding process. And the products prepared in this example were tested after dyeing, the results are shown in table 1.

Comparative example 1, commercial chinlon 66 fabric was pad-dyed using the acid dye pad-dyeing method described above. Experimental results show that chinlon 66 is poor in dye permeability after pad dyeing, cross section dye permeability tests show that the white core phenomenon occurs in fibers, and the tests after dyeing are shown in Table 3.

Example 2 pad dyeing of Nylon 56 Fabric with neutral dye (neutral deep yellow GL)

The padding liquor comprises the following components: preparing 100mL of dye solution which comprises neutral dye (neutral yellow GL), dyeing auxiliary agent (peregal O) and solvent (water); wherein the concentration of the neutral dye is 30g/L, and the concentration of the dyeing auxiliary agent is 20 g/L; the pH of the padding liquor was 6.8.

And (3) finishing the preparation of the dye solution, soaking the blended fabric in the dye solution for 5min by adopting a one-soaking one-rolling mode at room temperature, controlling the padder speed to be 40m/min, the pad pressure to be 0.22MPa and the pad liquor rate to be about 70 percent, baking the padded fabric for 25min at the temperature of 85 ℃, taking out a sample, washing the sample once in hot water at the temperature of 80 ℃, washing once in normal-temperature water, and air-drying to finish the pad dyeing process. And the products prepared in this example were tested after dyeing, the results are shown in table 3.

Comparative example 2, commercial chinlon 66 fabric was pad-dyed using the neutral dye pad-dyeing method described above. The nylon 66 surface had light color and poor dye penetration, and the test results after dyeing are shown in table 3.

Example 3 pad dyeing of Nylon 56 Fabric with reactive dye (reactive Brilliant blue D-RV)

The padding liquor comprises the following components: preparing 100mL of dye solution which comprises reactive dye (reactive brilliant blue D-RV), dyeing auxiliary agent (anhydrous sodium sulphate) and solvent (water); wherein the concentration of the reactive dye is 15g/L, and the concentration of the dyeing auxiliary agent is 20 g/L; the pH value of the padding liquor is 3.0.

The preparation of the dye solution is completed, under the condition of room temperature, a two-dipping two-rolling mode is adopted, the blended fabric is soaked in the dye solution for 5min, the padder speed is controlled to be 45m/min, the pad pressure is 0.2MPa, the pad liquor rate is about 75%, the pad dyed fabric is soaked in the fixing solution for one-rolling (the fixing solution method comprises the steps of preparing 100mL of fixing solution, 20g/L of sodium carbonate solution and soaking for 2min), the pad residual rate is controlled to be about 75%, a fixed sample is baked at 95 ℃ for 20min, then taken out and washed once in warm water at 50 ℃, taken out and washed once in cold water at normal temperature, soaped (3g/L of standard soap chips at 60 ℃ and 10min), taken out and washed once in warm water at 50 ℃ and washed once in cold water at normal temperature, and the pad dyeing is completed. And the products prepared in this example were tested after dyeing, the results are shown in table 3.

And (5) comparing example 2, pad dyeing the commercial nylon 66 fabric by adopting the reactive dye pad dyeing method. The nylon 66 surface had a light color and the test results after dyeing are shown in table 3.

Table 3 dyed fabric test results

The test results after dyeing the fabric shown in table 1 show that the apparent depth of the acid dye, the neutral dye and the reactive dye after pad dyeing the chinlon 56 is obviously higher than that of the chinlon 66 under the same low temperature (steaming or baking temperature) condition, and the color fastness of each item is good, which indicates that although the chinlon 66 can be dyed under the acid condition, the fiber dyeing effect is poor at low temperature, and the daily requirements cannot be met.

Claims

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

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 pad 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 pad dyeing method according to claim 1 or 2, characterized in that: the steps of pad dyeing with the acid dye or the neutral dye are as follows:

soaking the dyed object in padding liquor containing dye and dyeing auxiliary agent, padding by padder, controlling padding rate range, steaming or baking, and finally carrying out dyeing post-treatment;

the dye is the acid dye or the neutral dye.

4. The acid bath pad dyeing method according to claim 3, characterized in that: adopting a mode of one-dipping one-rolling, two-dipping two-rolling or multi-dipping multi-rolling;

the pad dyeing mode is one-dipping one-rolling, two-dipping two-rolling or multi-dipping multi-rolling;

after the pad dyeing, the mangling rate of the chinlon 56 fiber or the chinlon 56 fabric is 30-60%.

5. The acid bath pad dyeing method according to claim 3 or 4, characterized in that: in the padding liquor, the concentration of the dye is 5 g/L-40 g/L, and the concentration of the dyeing auxiliary agent is 1 g/L-60 g/L;

the specified rolling allowance is 50-80%;

the steaming or baking temperature is 50-100 ℃, and the time is 1-30 min.

6. The acid bath pad dyeing method according to any one of claims 3 to 5, characterized in that: when the reactive dye is adopted, the method is carried out according to the following 1) or 2):

the dye is the reactive dye.

7. The acid bath pad dyeing method according to claim 6, characterized in that: the pH value of the padding liquor is 2.5-6.8; adopting a mode of one-dipping one-rolling, two-dipping two-rolling or multi-dipping multi-rolling;

in the padding liquor, the concentration of the dye is 5-40 g/L, the concentration of the dyeing auxiliary agent is 1-60 g/L, and the concentration of the color fixing agent is 5-70 g/L;

the color fixing agent is a surfactant, a quaternary ammonium salt without surface activity, a resin type color fixing agent, a cross-linking color fixing agent or a formaldehyde-free color fixing agent;

in the padder, the rolling residual rate is controlled to be 50-80%, the padder speed is controlled to be 35-45 m/min, and the rolling pressure is controlled to be 0.18-0.25 MPa;

the baking or steaming temperature is 50-100 ℃, and the time is 1-30 min.

8. The acid bath pad dyeing method according to any one of claims 1 to 7, 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.

9. The acid bath pad dyeing method according to any one of claims 1 to 8, characterized in that: the neutral dye is a 1:2 type metal complex dye in an acidic mordant-containing dye.

10. The acid bath pad dyeing method according to any one of claims 1 to 8, 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.