KR101033471B1 - Dyeing methods for nano-fabrics - Google Patents

Abstract

The present invention relates to a method for dyeing nanofibers, and more specifically, 1) immersing nanofibers in a dyeing mixture, and dyeing by applying heat to the dyeing mixture in which nanofibers are immersed; 2) immersing the dyed nanofibers of step 1) in a fixing solution, followed by heat treatment; And 3) heat-treating the nanofibers of step 2).

The nanofiber dyeing method according to the present invention can be easily achieved without damaging the nanofibers dyeing the nanofibers that were difficult to dye conventionally. In addition, the dyeing fastness of the nanofibers is excellent, it can be usefully used in the textile dyeing industry.

Nano Fiber, Acid Dye

Description

Nano Fiber Dyeing Method {DYEING METHODS FOR NANO-FABRICS}

The present invention relates to a method for dyeing nanofibers, and more particularly to an invention in which a dyeing method for dyeing nanofibers is not easily improved by conventional dyeing methods.

Nanofibers are as smooth as skin, thinner and lighter than paper, breathing sweat, but not accepting foreign substances such as bacteria at all, and now the world is blowing a frenzy of developing nano-fabrics. This is because these nanofibers lead to dream fibers as ultra-fine yarns with diameters of only a few to several hundred nanometers (1 nanometer (nm) = 1 billionth of a meter). For reference, human hair is about 80,000 nm, and a sheet of paper is about 100,000 nm thick.

 These nanofibers with diameters of several hundreds of nanometers have a large surface area per unit volume and are capable of producing nanofibers of various surface properties, structures, and composite components, which are incomparable with conventional microfiber yarns. It is possible to overcome and create new functional products.

 It is known that nanofibers using such nanofiber manufacturing technology can be used as an ultra-high precision filter medium for environmental industry, electrical and electronic industry material, medical biomaterial, and high performance composite material.

 In the future, in order to create a variety of nanofibers, such as commercialization of the finished product, it is most important to maintain the intrinsic advantages of the fiber, in particular, it is required to have a good color fastness.

 On the other hand, in the case of the present invention screen printing, in the case of medium / post-woven fabrics Laura and rotary printing method is widely used, the printing method is limited to the general fabric / knitted fabric, and also possible to general microfiber (2.1 ㎛ diameter) Nanofibers with more fineness have the disadvantage that the dyeing itself is difficult.

 Therefore, there is still a need for a separate dyeing process for effective dyeing of nanofibers.

The present invention is to solve the above problems, to provide a method for dyeing nanofibers in a simple method.

In order to achieve the above object, the present invention comprises the steps of: 1) immersing the nanofibers in a dyeing mixture, and dyeing by applying heat to the dyeing mixture is immersed nanofibers; 2) immersing the dyed nanofibers of step 1) in a fixing solution, followed by heat treatment; And 3) heat treating the nanofibers of step 2).

First, step 1) is a step of dyeing by immersing the nanofibers in the dyeing mixture.

The dye mixture may be prepared by mixing an acid dye, an acid bacter salt, and the like. At this time, the dye mixture is 100 parts by weight of purified water acid dye 1 ~ 20% o.w.f. And acid bactericide may be added at 0.01 to 10% o.w.f. (on weight of fabric, dye amount added relative to fiber weight).

The acid dyes may be used leveling, milling, metal dyes and the like. The dyes may be used as appropriate, in order to obtain a single or desired color of the dyes of yellow, red, blue known in the art.

Leveling type dyes are characterized by low molecular weight, good migration and homogenization, but weak fastness compared to other dye groups. Generally, Ciba's Tectilon and Dythetelone Dystar Telon E, Nylanthrene of Yorkshire, and Rayon's Panacid E type group are suitable dyes for pale color.

Milling type dyes have a medium molecular weight of three dye groups, including half milling type, milling type and super milling type. It is a dye that needs fixing after dyeing.

Metal complex dye is a form of coordination of metals in dye molecules. It is characterized by high molecular weight and excellent fastness but weak leveling.

In addition, the acid bactericide may be alkylamine ethoxylate sulfate, polyoxyethylene, or the like.

At this time, the dye mixture of step 1) may be prepared and used at pH 2.0 ~ 6.0 using formic acid, acetic acid, acetate, sulfuric acid and the like. The pH is a pH range that can increase the stability of the dyeing mixture and increase the dyeability of the nanofibers.

In addition, the nanofibers are not particularly limited, and any nanofibers used in the art may be used without limitation. Preferably nylon or polyester-based nanofibers can be used.

In the present invention, the dyeing method is an optimized method for dyeing nanofibers, preferably, 0.5 to 2 while immersing the nanofibers in a dyeing mixture having an initial temperature of 10 to 40 ℃, and stirring them at 10 to 100 rpm, Heat is applied at ℃ / min, the temperature of the dye mixture mixture is heated to 60 ~ 120 ℃, it can be dyed by maintaining for 10 to 60 minutes in the elevated temperature range. At this time, the dyeing mixture is gradually heated to 0.5 to 2 ℃ / min, without damaging the nanofibers, it is possible to enhance the dyeing effect using the dyeing mixture.

In addition, when the dyeing temperature is less than 60 ℃, it is difficult to easily dye the nanofibers, if the dyeing temperature exceeds 120 ℃, even if the dyeing temperature is increased, the dyeing effect does not increase any more.

Next, step 2) is a step of applying a fixing agent to the nanofibers.

It is necessary to wash the nanofibers dyed through step 1) and to permanently fix the dyes. In order to permanently fix the dye, a conventional method in the art may be applied, and preferably, may be performed by immersing the nanofibers in the fixing solution. At this time, the fixing liquid may be added to the tannin series or synthetic series. More preferably, the tannin-based may be prepared by adding tannic acid, tin, etc., and the synthetic series by adding 0.5 to 5 parts by weight of phenol or bisphenol A to 100 ml of purified water. The fixing method using the fixing solution is to immerse the dyed nanofibers in the fixing solution, heat the fixing solution at 0.5 ~ 2 ℃ / min, to maintain the temperature of the fixing solution at 50 ~ 70 ℃ for 10 to 60 minutes Can be performed. At this time, the reason why the temperature of the fixing solution is gradually increased is that the fixing effect of dyeing can be enhanced without damaging the nanofibers.

In this step, when the temperature of the fixing liquid is less than 50 ℃, it is difficult to easily fix the nanofiber dyeing, if the temperature of the fixing liquid exceeds 70 ℃, the fixing efficiency further increases even if the fixing temperature rises I never do that.

Finally, step 3) is a step for increasing the fixing of the dyeing of the nanofibers.

Step 2) is a step of applying a fixing agent to the nanofibers, it is necessary to induce a reaction of the dyeing solution and the fixing solution can be dyed permanently fixed to the nanofibers. In step 2), the nanofibers reacted with the fixing solution may be taken out, placed in a reactor (Lab Tenter), and heated to perform a fixing step. Preferably, it may be carried out by applying heat to the nanofibers at 140 ~ 170 ℃. At this time, when the heating temperature is less than 140 ℃, it is difficult to induce the reaction of the dyeing solution and the fixing solution is difficult to easily fix the dyeing of the nanofiber, if the heating temperature exceeds 170 ℃ due to the high temperature, dyeing It is undesirable because it can cause damage to the nanofibers.

The present invention also provides a nanofiber dyed by the dyeing method.

The nanofibers are fibers made of ultra-fine fibers having diameters of only tens to hundreds of nanometers. The nanofibers are functional fibers capable of preventing the invasion of bacteria while preventing the inside of the sweat while preventing the passage of microparticles or bacteria. In the dyeing method according to the present invention, it is possible to obtain nanofiber dyeings having excellent fastness to dyeing of nanofibers in a simple process using acid dyes such as leveling type, milling type and metal type. Nanofiber dyeings according to the present invention maintains all the properties of the nanofibers, there is a feature that does not discolor the dyeing well.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

< Example  1> Preparation of Dyed Nanofibers 1

To dye nanofibers, milling dyes consisting of yellow 127, red 260 and blue 350 with CI (color index) are used with 8% owf and Albegal set (Huntsman) 1% owf. Was mixed with distilled water, and an appropriate amount of acetic acid was added to adjust the pH of the dye mixture to 6.0.

Nanofiber nylon 66 (400, 700, 1000 nm) was prepared in a size 10 × 10 cm, which was immersed in a 30 ℃ dye mixture. While stirring the dyeing mixture at 45 rpm, the temperature was raised to 1 ℃ / min, the dyeing mixture was maintained at 70 ℃ to proceed dyeing of nanofibers for 30 minutes.

After the dyeing reaction, the nanofibers were washed with hot water. In order to further fix the dyeing of the nanofibers, a fixing solution was prepared with a fixing agent (SCHEM, NYF) of 2.0 g / l and acetic acid 0.7 g / l, and the washed nanofibers were immersed therein. The fixing solution was heated to 1 ° C / min, and when the temperature of the fixing solution reached 70 ° C, the reaction was allowed to react for 20 minutes while maintaining this temperature. After the reaction, the immersed nanofibers were taken out, and the nanofibers were placed in a lab tenter. The lab tenter was heat treated at 150 ° C. to prepare dyed nanofibers.

< Example  2> Preparation of Dyed Nanofibers 2

Dyeing nanofibers were manufactured in the same manner as in Example 1, except that the dye mixture was prepared using a metal dye consisting of red 414 and blue 317 as an acid dye.

< Experimental Example  1> Measurement of dyeing degree according to dyeing temperature

Nanofiber nylon 66 (400, 700, 1000 nm) was prepared in a size 10 × 10 cm, it was immersed in 30, 40, 50, 60 ℃ dye mixture, respectively. The dyeing mixture was stirred for 30 minutes while stirring at 45 rpm per minute for dyeing.

After the dyeing reaction, the nanofibers were washed with hot water. In order to further fix the dyeing of the nanofibers, a fixing solution was prepared with a fixing agent of SCHEM-NYF 2.0 g / l and acetic acid 0.7 g / l, and the washed nanofibers were immersed therein. The fixing solution was heated to 1 ° C / min, and when the temperature of the fixing solution reached 70 ° C, the reaction was allowed to react for 20 minutes while maintaining this temperature. The results are shown in FIGS. 1 and 2.

In the figure, the K / S value is derived from the Kubelka-munk equation. The closer the reflectance is to 1, the closer the K / S is to 0, and the closer to 0 the reflectance, the K / S is to infinity. In other words, K / S refers to the apparent concentration, which refers to the concentration value visible after the actual dye is dyed to the dye. Therefore, dye concentration and K / S value increase proportionally.

As shown in Figure 1, the dye mixture of the millyl-type dye at the initial dyeing temperature K / S value of the dye according to the fineness of the nanofiber is stable at 40 ℃ by increasing the K / S value of the initial dye mixture at 30 ℃ Although the dye mixture of the metal-type dye is different depending on the fineness, there is no change in the temperature rise or rather the K / S value decreases at 60 ° C. In addition, it was found that the nanofibers having a fine thickness of 1000 nm showed a thicker dye concentration than the 400 nm nanofibers having a fine degree of fineness.

In addition, as shown in Figure 2, the dye mixture using the milling dye, the K / S value was decreased as the temperature of the final dye mixture is increased. In the dyeing mixture using the milling dye, the K / S value was stable up to 90 ° C. The K / S value was decreased at 100 ° C. In addition, the dye mixture using the metal dye was increased K / S value from 80 ℃ can be seen a phenomenon that the dye dye is released without the stability of the dye.

The nanofiber dyeing method according to the present invention can be easily achieved without damaging the nanofibers dyeing the nanofibers that were difficult to dye conventionally. In addition, the dyeing fastness of the nanofibers is excellent, it can be usefully used in the textile dyeing industry.

1 and 2 are the results of measuring the difference in dyeability according to the type of nanofibers and the temperature of the dye solution.

Claims (12)

1) immersing the nanofibers in the dyeing mixture, and dyeing by applying heat to the dyeing mixture is immersed nanofibers; 2) immersing the dyed nanofibers of step 1) in a fixing solution, followed by heat treatment; And 3) heat-treating the nanofibers of step 2); Nanofiber dyeing method comprising a. The method of claim 1, wherein the dyeing mixture of step 1) is a nanofiber dyeing method, characterized in that prepared by mixing an acid dye and an acid bacter salt. According to claim 2, wherein the dyeing mixture is 100 parts by weight of purified water acid dyes 1 ~ 20% o.w.f. And acid bactericide is added at 0.01 to 10% o.w.f. The nanofiber dyeing method according to claim 3, wherein the acid dye is one dye selected from the group consisting of leveling type, milling type and metal type. The nanofiber dyeing method according to claim 2, wherein the acid bactericide is alkylamine ethoxylate sulfate or polyoxyethylene. The nanofiber dyeing method according to claim 1, wherein the dyeing mixture of step 1) is prepared at a pH of 2.0 to 6.0 using one selected from the group consisting of formic acid, acetic acid, acetate and sulfuric acid. The nanofiber dyeing method according to claim 1, wherein the initial temperature of the dyeing mixture of step 1) is 10 to 40 ° C. The method of claim 1, wherein in step 1) while stirring the dyeing mixture at 10 ~ 100 rpm, heat is applied at 0.5 ~ 2 ℃ / min, maintaining the temperature of the dyeing mixture at 60 ~ 120 ℃ for 10 to 60 minutes Nanofiber dyeing method, characterized in that. The method of claim 1, wherein the step 2) nanofiber dyeing method, characterized in that the fixing solution is 50 ~ 70 ℃. The method of claim 1, wherein the fixing solution of step 2) is heated to 0.5 ~ 2 ℃ / min, the nanofiber dyeing method, characterized in that to maintain the temperature of the fixing solution at 50 ~ 70 ℃ for 10 to 60 minutes . The nanofiber dyeing method according to claim 1, wherein the heat treatment of the nanofibers in step 3) is performed at 140 to 170 ° C. The nanofibers dyed by the dyeing method according to any one of claims 1 to 11.

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