High-fastness brocade silk and dyeing processing method and application thereof

Abstract

The invention discloses high-fastness brocade silk as well as a dyeing processing method and application thereof. The method comprises the following steps: (1) soaking the brocade silk in a polyamide hydrolase treatment solution for pretreatment; (2) dipping the brocade silk treated in the step (1) in a solution of carboxyl-containing phenol micromolecules, and grafting the carboxyl-containing phenol micromolecules on the surface of the nylon fiber; and (3) padding the brocade silk treated in the step (2) with an alkaline agent, and then dipping the brocade silk in a diazonium salt solution to realize in-situ coloring of the brocade silk. The method comprises the following steps: firstly, treating brocade silk by virtue of polyamide hydrolase to hydrolyze part of amido bonds on the surfaces of polyamide fibers to generate amino groups; then, by means of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, phenolic micromolecules are grafted on the surface of the polyamide fiber, and the polyamide silk containing the coupling component is prepared; finally, the brocade silk containing the coupling component is soaked in a diazonium salt solution, azo dye is formed through a coupling reaction, and low-energy-consumption and high-fastness brocade silk dyeing processing is achieved.

Description

Technical Field

[0001] The invention relates to dyeing and finishing of textiles, in particular to a high-fastness brocade silk and a dyeing method and application thereof. Background Art

[0002] Nylon fibers mainly include nylon 6 and nylon 66, which are commonly used synthetic fiber varieties. Compared with polyester fibers, nylon fibers have higher wear resistance, excellent elasticity and strength, and the standard moisture regain of nylon fibers is higher than that of polyester fibers. Textiles processed with nylon fibers as raw materials are widely used in sportswear, outdoor textiles (such as tents, paragliders, parachutes) and many other scenarios.

[0003] The glass transition temperature of nylon fiber itself is lower than that of polyester, so dyeing does not need to be carried out under high temperature and pressure, and dyeing can be completed under normal pressure boiling dyeing. However, the hygroscopicity of nylon fiber mainly depends on the amide bond in its macromolecular chain, and the number of its reactive groups (amino groups) is relatively small. Therefore, when dyeing with reactive dyes, the number of covalent bonds that can be formed between the dye and the fiber is small, making it difficult to dye nylon fabrics dark. At present, nylon fiber products are mostly dyed with weak acid dyes, generally under weak acid conditions, through hydrogen bonds, van der Waals forces and a small number of ionic bonds. In addition, due to the lack of covalent bonds between weak acid dyes and nylon fibers, the color fastness of fiber products is relatively low, which affects the quality of printing and dyeing products with nylon as raw materials.

[0004] Therefore, how to improve the dyeing method of nylon silk using nylon filament as raw material to increase the dyeing depth of nylon silk and obtain higher color fastness is a technical problem of dyeing and finishing that needs to be solved at present. Summary of the invention

[0005] In view of the above-mentioned problems of insufficient dyeing depth and color fastness of nylon silk, the present invention provides a high-fastness nylon silk and a dyeing processing method and application thereof. The method first grafts phenolic small molecules on the surface of nylon fiber, and then couples with diazonium salt to achieve in-situ coupling coloration of nylon silk under low temperature conditions, thereby achieving low-energy consumption and high-fastness nylon silk dyeing processing.

[0006] In order to achieve the above object, the present invention provides a high-fastness brocade silk dyeing processing method, which comprises the following steps: (1) Pre-treating nylon fibers by immersing them in a polyamide hydrolase treatment solution to hydrolyze the amide bonds in the nylon fibers to introduce amino groups on the fiber surface; (2) immersing the nylon fiber treated in step (1) in a solution of carboxyl-containing phenolic small molecules, and grafting the carboxyl-containing phenolic small molecules on the surface of the nylon fiber with the aid of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; (3) The brocade silk treated in step (2) is dipped in an alkali agent and then immersed in a diazonium salt solution, and the in-situ coloration of the brocade silk is achieved through a coupling reaction between the diazonium salt and the phenolic small molecules grafted on the surface of the brocade silk fiber.

[0007] In the above technical scheme, nylon silk is first treated with polyamide hydrolase to hydrolyze part of the amide bonds on the surface of nylon fiber to produce amino groups; then, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride is used to graft phenolic small molecules on the surface of nylon fiber to prepare nylon silk containing coupling components; finally, the nylon silk containing coupling components is immersed in a diazonium salt solution to form azo dyes through coupling reactions, thereby realizing low-energy consumption and high-fastness nylon silk dyeing processing. 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride is used to connect the carboxyl groups on the phenolic small molecules and the amino groups on the nylon.

[0008] In one embodiment of the present invention, in step (1), the concentration of polyamide hydrolase in the treatment solution is 2-4 U / mL, and the treatment conditions are: temperature 45-50°C, pH range 7-8, treatment time 2-3 h, and bath ratio 1:10-15.

[0009] In one embodiment of the present invention, in step (2), the composition of the solution of carboxyl-containing phenolic small molecules is: phenolic small molecules 7.5-10 g / L, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 4-8 g / L, N -Hydroxysuccinimide 3~6 g / L; treatment conditions: temperature 25~30 ℃, pH range 5~7, treatment time 3~6 h, bath ratio 1:10~15.

[0010] In one embodiment of the present invention, the phenolic small molecule package is selected from one or more of caffeic acid, ferulic acid, gallic acid and syringic acid. The phenolic small molecule structure contains both carboxyl and phenolic hydroxyl groups. The carboxyl group is conducive to the nylon medium, and the phenolic hydroxyl group is conducive to subsequent coupling coloration as a site.

[0011] In one embodiment of the present invention, in step (3), the brocade silk is soaked in an alkali agent process as follows: caustic soda 0.05-0.2 g / L, and a milling rate of 100%.

[0012] In one embodiment of the present invention, in step (3), the preparation process of the diazonium salt solution is: 7.5-10 g / L of aromatic amine compound, 2.5-4 g / L of hydrochloric acid, 5-10 g / L of sodium nitrite, temperature 0-5°C, treatment time 30-45 min, and urea is added after the reaction to remove excess nitrite until the starch-potassium iodide test paper turns light blue.

[0013] In one embodiment of the present invention, the aromatic amine compound is selected from aniline, p-nitroaniline, methoxyaniline, anisidine, p-aminobenzenesulfonic acid or α-naphthylamine.

[0014] In one embodiment of the present invention, in step (3), the in-situ color-producing conditions for the coupling reaction between the diazonium salt and brocade silk are: 0-5°C, treatment time 5-15 min, and bath ratio 1:10-15.

[0015] The second aspect of the present invention provides brocade silk obtained by the dyeing method described above.

[0016] The third aspect of the present invention provides the use of the above-mentioned brocade silk in the preparation of functional textiles.

[0017] Beneficial effects: The present invention firstly treats nylon silk with the aid of polyamide hydrolase to hydrolyze part of the amide bonds on the surface of the nylon fiber to produce amino groups; then, with the aid of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, phenolic small molecules are grafted on the surface of the nylon fiber to prepare nylon silk containing coupling components; finally, the nylon silk containing coupling components is immersed in a diazonium salt solution to form azo dyes through coupling reactions, thereby realizing a method for dyeing nylon silk with low energy consumption and high fastness. Compared with dyeing nylon silk with active dyes (bonded by covalent bonds, difficult to dye deep) and weak acid dyes (bonded by hydrogen bonds, van der Waals forces and ionic bonds, poor fastness to dark colors), the nylon silk dyeing method of the present invention has the following advantages: (1) Improved fabric dyeing depth. The amide bonds on the fiber surface are partially hydrolyzed by polyamide hydrolase, which increases the number of amino groups on the fiber surface and improves the fiber reactivity. On this basis, carboxyl-containing phenolic small molecules are grafted onto nylon fibers, and in-situ coloration of the fabric surface is achieved through coupling with diazonium salts. The dyeing depth of nylon silk is greatly increased compared with that of reactive dyes.

[0018] (2) The fabric has good color fastness. Compared with the use of weak acid dyes to dye nylon silk products, the method of the present invention achieves in-situ dyeing of nylon silk by coupling diazonium salt with phenolic small molecules grafted on the surface of nylon fibers; the dye generated in the process is covalently bonded to the fiber, and the obtained nylon silk has good color fastness.

[0019] (3) Low energy consumption in the dyeing process. Compared with the traditional brocade silk dyeing conditions of high temperature or near boiling, the brocade silk of the present invention can achieve in-situ coloration on the surface of the fabric through diazotization coupling reaction under low temperature conditions. The production energy consumption in the dyeing process is low, which has significant technical advantages in energy saving and consumption reduction. DETAILED DESCRIPTION

[0020] The specific implementation of the present invention is described in detail below in conjunction with the examples. It should be understood that the specific implementation described herein is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0021] Embodiment 1: (1) Enzymatic pretreatment of nylon: Polyamide hydrolase was used to pretreat nylon silk (weight 65 g / m 2 ) pretreatment to introduce amino groups on the fiber surface, followed by washing and drying; the treatment process is: polyamide hydrolase 2 U / mL, treatment at 45°C, pH 7 for 2 h, bath ratio 1:10.

[0022] (2) Grafting phenol coupling component: The brocade silk treated in step (1) is immersed in a caffeic acid solution, and caffeic acid is grafted on the fiber surface with the aid of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. After treatment, the fiber is washed and dried. The treatment process is: caffeic acid 7.5 g / L, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 4 g / L, N -Hydroxysuccinimide 3 g / L, treated at 25℃, pH 5 for 6 h, bath ratio 1:10.

[0023] (3) In-situ coupling reaction color development: The brocade silk treated in step (2) is dipped into an alkali agent, and then immersed in a diazonium salt solution to achieve in-situ color development, and finally the fabric is washed and dried; wherein the alkali padding process is: 0.05 g / L caustic soda, and the rolling rate is 100%; the diazonium salt solution preparation process is: 7.5 g / L aniline, 2.5 g / L hydrochloric acid, and 5 g / L sodium nitrite, react at 0-5°C for 30 min, and after the reaction, urea is added to remove excess nitrite until the starch-potassium iodide test paper is light blue; the coupling conditions of diazonium salt and brocade silk are: treatment at 0-5°C for 5 min, and a bath ratio of 1:10.

[0024] Embodiment 2: (1) Enzymatic pretreatment of nylon: Polyamide hydrolase was used to pretreat nylon silk (weight 82 g / m 2 ) pretreatment to introduce amino groups on the fiber surface, followed by washing and drying; the treatment process is: polyamide hydrolase 4 U / mL, treatment at 50℃, pH 8 for 3 h, bath ratio 1:15.

[0025] (2) Grafting phenol coupling component: The brocade silk treated in step (1) is immersed in a ferulic acid solution, and ferulic acid is grafted on the surface of the fiber with the aid of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. After treatment, the fiber is washed and dried. The treatment process is as follows: ferulic acid 10 g / L, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride 8 g / L, N-Hydroxysuccinimide 6 g / L, treated at 30℃, pH 7 for 12 h, bath ratio 1:15.

[0026] (3) In-situ coupling reaction color development: The brocade silk treated in step (2) is dipped into an alkali agent, and then immersed in a diazonium salt solution to achieve in-situ color development, and finally the fabric is washed and dried; wherein the alkali padding process is: 0.2 g / L caustic soda, and the rolling rate is 100%; the diazonium salt solution preparation process is: 10 g / L p-aminobenzenesulfonic acid, 4 g / L hydrochloric acid, and 10 g / L sodium nitrite, react at 0-5°C for 45 min, and after the reaction, urea is added to remove excess nitrite until the starch-potassium iodide test paper turns light blue; the coupling conditions of diazonium salt and brocade silk are: treatment at 0-5°C for 15 min, and a bath ratio of 1:15.

[0027] Embodiment 3: (1) Enzymatic pretreatment of nylon: Polyamide hydrolase was used to pretreat nylon silk (weight 75 g / m 2 ) pretreatment to introduce amino groups on the fiber surface, followed by washing and drying; the treatment process is: polyamide hydrolase 3 U / mL, treatment at 45°C, pH 7 for 2.5 h, bath ratio 1:10.

[0028] (2) Grafting phenol coupling component: The brocade silk treated in step (1) is immersed in a mixed solution of gallic acid and syringic acid, and caffeic acid is grafted on the fiber surface with the help of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride. After treatment, the fiber is washed and dried; the treatment process is: gallic acid 4.5 g / L, syringic acid 4.5 g / L, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 6 g / L, N -Hydroxysuccinimide 4 g / L, treated at 25℃, pH 6 for 4 h, bath ratio 1:10.

[0029] (3) In-situ coupling reaction color development: The brocade silk treated in step (2) is dipped into an alkali agent, and then immersed in a diazonium salt solution to achieve in-situ color development, and finally the fabric is washed and dried; wherein the alkali agent dipping process is: 0.1 g / L caustic soda, and the rolling rate is 100%; the diazonium salt solution preparation process is: 9 g / L α-naphthylamine, 3 g / L hydrochloric acid, and 7 g / L sodium nitrite, reacting at 0-5°C for 35 min, and after the reaction, urea is added to remove excess nitrite until the starch-potassium iodide test paper is light blue; the coupling conditions of diazonium salt and brocade silk are: treatment at 0-5°C for 5 min, and a bath ratio of 1:10.

[0030] Comparative Example 1: The brocade silk without any treatment in Example 1.

[0031] Comparative Example 2: In implementation 1, step (1) is omitted and steps (2) and (3) are performed only. Other conditions or descriptions are consistent with those in Example 1.

[0032] Comparative Example 3: The method of implementing 1 is to skip step (2) and only carry out steps (1) and (3). Other conditions or descriptions are the same as those in Example 1.

[0033] Comparative Example 4: The method of implementing 1 is to skip step (3) and only carry out steps (1) and (2). Other conditions or descriptions are the same as those in Example 1.

[0034] Comparative Example 5: The brocade silk of the same specifications as in Example 1 was dyed with weak acid dyes, and the dyeing process conditions were: weak acid ruby ​​​​1g / L, pH 6, dyeing at 95°C for 60min, and then washing and drying the fabric.

[0035] Comparative Example 6: The brocade silk without any treatment in Example 2.

[0036] Comparative Example 7: In implementation 2, step (1) is omitted and steps (2) and (3) are performed only. Other conditions or descriptions are consistent with those in Example 2.

[0037] Comparative Example 8: In implementation 2, step (2) is omitted and only steps (1) and (3) are performed. Other conditions or descriptions are consistent with those in Example 2.

[0038] Comparative Example 9: The method of implementing Example 2 is to skip step (3) and only carry out steps (1) and (3). Other conditions or descriptions are the same as those of Example 2.

[0039] Comparative Example 10: The brocade silk of the same specifications as in Example 2 was dyed with weak acid dyes, and the dyeing process conditions were: weak acid sauce ruby ​​​​1.45 g / L, pH 6, dyeing at 95°C for 60 minutes, and then washing and drying the fabric.

[0040] The performance indicators of the samples in the above-mentioned Examples 1-2 and Comparative Examples 1-10 were measured respectively, and the method was as follows: The dyeing depth K / S value of the brocade silk sample surface under D65 light source and 10° field of view was measured by spectrophotometer; the washing fastness (original color change grade) and wet rubbing fastness (backing staining grade) of the dyed brocade silk sample were measured with reference to GB / T 3921-2008 and GB / T3920-2013; the drape coefficient was measured with reference to GB / T 23329-2009 to evaluate the effect of dyeing on the sample feel. The smaller the drape coefficient, the better the drape of the fabric and the softer the feel. The results are shown in Table 1.

[0041] Table 1 Performance test results

[0042] From Table 1, we can see that: a. The nylon silk (Example 1, Example 2, Example 3) dyed by the method of the present invention has a higher color depth K / S value than the samples in other comparative examples, and has better washing and rubbing fastness, indicating that the hydrolase can increase the reactivity of nylon, which is beneficial to the grafting of phenolic small molecules on the fiber surface, providing conditions for the diazonium salt coupling coloration; the azo dye formed by coupling is combined with the fiber in a covalent bond manner, ensuring that the nylon silk dyeing product has good color fastness; the fabric drape coefficient is similar to that of the undyed samples (Comparative Example 1, Comparative Example 6), indicating that the dyeing method has little effect on the feel of the fabric.

[0043] b. The samples (Comparative Example 2 and Comparative Example 7) that were not treated with step (1) but only with steps (2) and (3) had a lower color depth K / S value, which was similar to that of the untreated nylon silk samples (Comparative Example 1 and Comparative Example 6). The reason for this is that the number of amino groups on the surface of the nylon fiber that was not pretreated by the enzyme method was relatively small, resulting in a relatively small number of phenolic small molecules that could be grafted onto the fiber surface during the treatment in step (2), causing the treatment in step (3) to fail to produce color by coupling with the diazonium salt. Since the color of the nylon silk samples after treatment was lighter, the fastness grade was also higher. The drape of the fabric was similar to that of the untreated samples.

[0044] c. The samples (Comparative Example 3 and Comparative Example 8) that were not treated in step (2) but only treated in steps (1) and (3) had a lower color depth K / S value, which was basically similar to that of the untreated brocade silk samples (Comparative Example 1 and Comparative Example 6). The reason for this is that without the treatment in step (2), the fiber surface lacked sites that could react with the diazonium salt, resulting in no coupling reaction on the fiber surface during the treatment in step (3) (no azo dye was formed).

[0045] d. The samples (Comparative Example 4 and Comparative Example 9) that were not treated with step (3) but only with steps (1) and (2) had lower color depth K / S values. This is because only phenolic reaction sites were grafted onto the surface of the nylon fiber. However, since step (3) was not performed (i.e., the fiber surface did not couple with the diazonium salt to form an azo dye), the surface color depth values ​​of the nylon silk samples were lower.

[0046] e. The color depth K / S values ​​of the samples (Comparative Example 5 and Comparative Example 10) dyed with the same specifications of brocade silk as the raw material and the weak acid dyeing process are similar to those of the samples in Example 1, Example 2, and Example 3, respectively; but the washing fastness and rubbing fastness are significantly lower than those of the samples in Example 1, Example 2, and Example 3. The reason is that the weak acid dye is mainly combined with the fiber through hydrogen bonds, van der Waals forces, and ionic bonds, and the bonding fastness between the dye and the fiber is not as good as the covalent bond formed between the dye and the fiber by the azo dye described in the present invention. It can be seen that the method described in the present invention has better bonding fastness than the traditional weak acid dyeing method under the same color depth conditions.

[0047] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0048] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0049] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A high-fastness brocade silk dyeing process, characterized in that: The steps include: (1) Pre-treating nylon fibers by immersing them in a polyamide hydrolase treatment solution to hydrolyze the amide bonds in the nylon fibers to introduce amino groups on the fiber surface; (2) immersing the nylon fiber treated in step (1) in a solution of carboxyl-containing phenolic small molecules, and grafting the carboxyl-containing phenolic small molecules on the surface of the nylon fiber with the aid of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; (3) The brocade silk treated in step (2) is dipped in an alkali agent and then immersed in a diazonium salt solution, and the in-situ coloration of the brocade silk is achieved through a coupling reaction between the diazonium salt and the phenolic small molecules grafted on the surface of the brocade silk fiber.

2. The dyeing method according to claim 1, characterized in that In step (1), the concentration of polyamide hydrolase in the treatment solution is 2-4 U / mL, and the treatment conditions are: temperature 45-50°C, pH range 7-8, treatment time 2-3 h, and bath ratio 1:10-15.

3. The dyeing method according to claim 1, characterized in that In step (2), the composition of the solution of carboxyl-containing phenolic small molecules is: phenolic small molecules 7.5-10 g / L, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 4-8 g / L, N -Hydroxysuccinimide 3~6 g / L; treatment conditions: temperature 25~30 ℃, pH range 5~7, treatment time 3~6 h, bath ratio 1:10~15.

4. The dyeing method according to claim 2, characterized in that: The phenolic small molecules are selected from one or more of caffeic acid, ferulic acid, gallic acid and syringic acid.

5. The dyeing method according to claim 1, characterized in that: In step (3), the process of soaking the brocade silk in an alkali agent is as follows: caustic soda 0.05-0.2 g / L, and the rolling rate is 100%.

6. The dyeing method according to claim 1, characterized in that: In step (3), the preparation process of the diazonium salt solution is: 7.5-10 g / L of aromatic amine compound, 2.5-4 g / L of hydrochloric acid, 5-10 g / L of sodium nitrite, temperature 0-5°C, treatment time 30-45 min, and urea is added after the reaction to remove excess nitrite until the starch-potassium iodide test paper turns light blue.

7. The dyeing method according to claim 6, characterized in that: The aromatic amine compound is selected from aniline, p-nitroaniline, methoxyaniline, anisidine, p-aminobenzenesulfonic acid or α-naphthylamine.

8. The dyeing method according to claim 1, characterized in that: In step (3), the in-situ color-producing conditions for the coupling reaction between the diazonium salt and brocade silk are: 0-5°C, treatment time 5-15 min, and bath ratio 1:10-15.

9. Brocade silk obtained by the dyeing method according to any one of claims 1 to 8.

10. Use of the brocade silk according to claim 9 in preparing functional textiles.

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