KR20180115429A - Dyeing method of polyolefin-based fabric - Google Patents

Abstract

A method for dyeing a polyolefin-based fabric comprises the following steps: diluting a dyeing solution containing a solvent dye and acetone with water to prepare a dyeing solution; putting a fabric composed of polyolefin fibers to the dyeing solution and then dyeing the same; cleaning the dyed fabric; and drying the same.

Description

DYEING METHOD OF POLYOLEFIN-BASED FABRIC [0002]

The present invention relates to a method of dyeing polyolefin fabrics, and more particularly to a method of dyeing polyolefin fabrics having improved dyeability of highly hydrophobic polyolefin fabrics.

Olefins are aliphatic unsaturated hydrocarbons, which are compounds with carbon and carbon double bonds (C = C bonds). Polyethylene (PE), polypropylene (PP), ultra high molecular weight polyethylene (UHMWPE) . The molecular chain of polyethylene has a linear structure, and it has the advantages of excellent abrasion resistance, high tensile strength, self lubrication, crack resistance, chemical stability and small friction coefficient, and it can be applied to various industrial fields such as bulletproof vests, military complexes and bulletproof helmets . In addition, the polyethylene fiber has a specific gravity of 0.93 to 0.98, which is low in density and lightweight, and has been studied as a variety of lightweight materials. In addition to the above-mentioned applications, it can be used for security protective clothing, sporting goods such as clothing, shoes and accessories . However, polyethylene fibers having high strength have a problem in that dyeing work is very difficult because the crystal structure is dense and tightly formed so that the dispersion dye can not easily penetrate into the crystal structure during the dyeing process and the dispersion dye is not smoothly have. In order to solve such a problem, the olefin fibers, which are synthetic fibers, are subjected to a quenching process to impart glue property and irregularity of the natural fibers, thereby facilitating the penetration of the dye into the fibers, and then performing the dyeing process.

Patent Document KR2014-0185757 related to high-strength polyolefin-based fiber dyeing by the post-dyeing method is a method of dyeing at a dyeing temperature of 80 to 100 DEG C in a mixing bath containing a solvent dye, water and alcohols, followed by reduction washing and drying at 130 to 170 DEG C A method of dyeing polyolefin-based fibers has been described.

The Chinese patent CN 2013-10744307 relates to a method for dyeing ultrahigh molecular weight polyethylene fibers, which is an improvement of the chemical coloring method of highly chemically inert ultrahigh molecular weight polyethylene. The dispersion dye is added at a temperature of 50 to 60 ° C and the temperature is slowly increased to 133 ℃ for 30 minutes to dye the ultrahigh molecular weight polyethylene.

Korean Patent KR 2009-0053287 relates to a high-throughput dyeing method of polypropylene fabrics, which comprises pretreating a chlorinated polypropylene fabric, dyeing it with a disperse dye, and acid-reducing the washed dye to improve the leveling effect and fastness. The method of dyeing the fabric was proposed.

Korean Patent KR 2011-0097418 discloses a method for dyeing ultrahigh molecular weight polyethylene fibers and a glove made of dyed fibers by using the four steps of processing, soft and binding, salt fixing, dyeing and reduction washing steps A method capable of having excellent durability and fastness has been described.

Nevertheless, there is a problem that the known dyeing method has a limitation in maximizing the dyeability of the polyolefin-based fabric, that is, maximizing the dyeing amount, and the tensile strength and the like of the polyolefin-based fabric in the dyeing step is lowered.

It is an object of the present invention to provide a method of dyeing a polyolefin-based fabric capable of maximizing the salt loading of the polyolefin-based fabric.

A method for dyeing a polyolefin-based fabric for an object of the present invention comprises the steps of: preparing a dyeing solution by diluting a salt solution containing a solvent dye and acetone with water; Adding a fabric composed of polyolefin fibers to the dyeing solution to dye; Cleaning the dyed fabric; And drying.

In one embodiment, the dyeing step may be performed at less than 2 hours at a temperature of less than or equal to 130 < 0 > C.

In one embodiment, the content of acetone in the saline solution may be up to 40% by weight based on the total weight of the saline solution.

In one embodiment, when the solvent dye is Solvent Yellow 56, the content of acetone in the saline solution is 5 wt% based on the total weight of the saline solution, and when the solvent dye is Solvent Red 24, the content of acetone in the saline solution is And the solvent dye is Solvent Blue 14, the content of acetone in the saline solution may be 20 wt% based on the total weight of the saline solution.

In one embodiment, the cleaning step removes residual solvent dyes that do not adhere to the dyed polyolefinic fabrics using acetone, and the dyeing method does not include a separate reduction cleaning step.

According to the dyeing method of the polyolefin-based fabric of the present invention described above, various kinds of colors can be dyed on a polyolefin-based fabric composed of polyolefin fibers. Also, the size of the solvent dye can be controlled by controlling the organic solvent content without the dispersant, and the polyolefin-based fabric having the dyeing property and the excellent fastness at low temperature can be dyed.

FIG. 1 is a photograph showing the results of dyeing 200 denier UHMWPE filaments at different dyeing temperatures using a dispersing agent.
FIG. 2 is a photograph showing the results of dyeing 200 denier UHMWPE filaments dyed at different dyeing temperatures under the condition of no dispersing agent according to the present invention, and FIG. 3 is a view showing the results of analysis of salt loading and tensile strength of each sample of FIG. 2 .
FIG. 4 is a photograph showing the results of dyeing 200 denier UHMWPE filaments stained for each dyeing time, and FIG. 5 is a graph showing the results of analysis of salt loading and tensile strength of each of the samples of FIG.
FIG. 6 is a photograph showing the results of dyeing Solvent 97 and Solvent 14 by the dyeing temperature.
FIG. 7 shows photographs of dyeing results of 200 denier UHMWPE filaments dyed by dye concentration, and FIG. 8 is a diagram showing the results of analysis of the salt amount of each of the samples of FIG.
FIG. 9 is a photograph showing the result of dyeing 200 denier UHMWPE filament according to acetone content, and FIG. 10 is a diagram showing the result of analysis of the salt amount of each sample of FIG.
FIG. 11 is a photograph of a sample stained using Solvent Blue 97 according to an acetone content, and FIG. 12 is a view showing a tensile strength and strength analysis result of each sample of FIG.
13 is a photograph showing the results of staining of UHMWPE filaments stained with a three-color solvent dye.
FIG. 14 is a photograph showing the results of dyeing 200 denier HTPE filaments according to dyeing temperature, and FIG. 15 is a diagram showing the results of analysis of salt loading and tensile strength of each sample of FIG.
FIG. 16 is a photograph showing the results of dyeing 200 denier HTPE filaments per dyeing time, and FIG. 17 is a diagram showing the results of analysis of salt loading and tensile strength of each sample of FIG.
FIG. 18 is a photograph showing the result of dyeing 200 denier HTPE filament according to dye concentration, and FIG. 19 is a diagram showing the result of analysis of the salt amount of each sample of FIG. 18.
FIG. 20 is a photograph showing the results of dyeing 200 denier HTPE filaments according to acetone content, and FIG. 21 is a diagram showing the results of analysis of salt loading and tensile strength of each sample of FIG. 20.
22 shows photographs of 200 denier HTPE fabric dye samples and HTPE / PET blend fabric samples.
23 is a photograph showing photographs of each of the surface and cross-section of a 200 denier HTPE fabric dyed sample.
FIG. 24 is a view showing photographs of 100 denier grade filament three-color dyed samples for each dyeing temperature, and FIG. 25 is a view showing the results of analysis of salt loading and tensile strength of each sample of FIG.
FIG. 26 is a view showing photographs of 100 denier grade filament three-color-stained samples by dying time, FIG. 27 is a view showing a result of analysis of the salt amount of each sample of FIG. 26, FIG. 28 is a graph showing tensile strength Fig.
FIG. 29 shows photographs of 100 denier grade filament three-color dyed samples by dye concentration, and FIG. 30 is a diagram showing the results of analysis of the salt amount of samples of FIG. 29.
31 is a photograph showing a 100-denier grade fabric three-color-stained samples.

In the present invention, in order to dye various kinds of polyolefin fibers, the dyes were selected through calculation of LogP value of the three-color solvent dye, and the dye was dissolved using acetone, and distilled water was added thereto to control the particle size and bath ratio of the dye. Dyeing temperature, dyeing time and acetone content were evaluated on dyeability and tensile strength. In addition, cross-sectional photographs and surface photographs of the dyed polyolefin fibers were taken to investigate the state of internal color development.

Preparation of dyes and reagents

For dyeing polyolefin fibers (200 denier UHMWPE (Ultra High Molecular Weight Polyethylene), 400 denier, 200 denier, 100 denier HTPE (High Tenacity polyethylene) fabric using three primary color solvent dyes, the three primary color solvent dyes were CI Solvent Blue 14 (C24H30N2O2, Aldrich Chemical Co.), CI Solvent Red27 (C26H24N4O, Aldrich Chemical Co.) and Solvent Yellow 56 (C16H19N3, Tokyo Chemical Ltd.) were used as the other reagents. The third distilled water was used.

Selection of dye

High strength polyethylene filament (HTPE) has a strong hydrophobic property and it is known that it is very difficult to uniformly dye using a general disperse dye. Therefore, in order to dye high-strength polyethylene filaments, various kinds of three-color solvent dyes having high hydrophobicity and high solubility in organic solvents were selected and the log P value of each dye was calculated. LogP represents the partition coefficient between water and octanol and is an indicator of the degree of hydrophobicity of the organic composition. ALOGP, CLOGP and ALOGPS methods are most widely used to calculate experimental values, semi-experimental values and theoretical values. ALOGP (Atom-based method) has the merit of simple computation as a method of arithmetically adding atomic units to the hydrophobicity of chemical substances, but it has disadvantage that error correction is not applied. CLOGP (Fragmental method) is the most widely used method with ALOGP. It divides the molecules into atomic groups according to certain rules and calculates them by applying correction factor. It can calculate more accurate than ALOGP for small molecules with less than 30 atoms However, it is known that errors occur when the number of atoms is 30 or more. In addition, ALOGPS is a method of calculating the physicochemical properties by applying an electrical topological indicator (E-state indication), which is more accurate and faster than ALOGP and CLOGP. Accordingly, in order to select a three-color solvent dye suitable for high-strength polyethylene filament (HTPE) dyeing, various anthraquinone blue, monoazo yellow and diazo red are selected and the log P value Respectively. In order to reduce the error caused by the log P value, the average value of the log P values calculated by the three methods is calculated and shown in Table 1. As described above, the log P value of the three-color solvent dye was calculated and the C.I. Solvent Blue 14, C.I. Solvent Yellow 56 and C.I. Solvent Red 27 were selected, and the structural formula of the three-color solvent dye is shown in Table 1 below.

Color Chromophore Dyes ALOGP CLOGP ALOGPS Average Red Diazo C. I. Solvent Red 3 5.29 5.69 5.42 5.47 C. I. Solvent Red 23 7.51 6.84 6.01 6.79 C. I. Solvent Red 25 8.49 7.84 6.70 7.68 C. I. Solvent Red 26 8.98 8.34 6.84 8.05 C. I. Solvent Red 27 9.46 8.83 6.85 8.38 Yellow Monoazo C. I. Solvent Yellow 2 4.76 4.46 4.63 4.62 C. I. Solvent Yellow 3 4.64 4.30 4.35 4.43 C. I. Solvent Yellow 4 4.66 4.53 4.78 4.66 C. I. Solvent Yellow 7 4.08 3.96 3.82 3.95 C. I. Solvent Yellow 12 5.06 4.95 4.39 4.80 C. I. Solvent Yellow 14 5.08 5.13 4.88 5.03 C. I. Solvent Yellow 56 5.43 5.52 5.45 5.47 Blue Anthraquinone C. I. Solvent Blue 11 3.87 6.65 4.66 5.06 C. I. Solvent Blue 14 4.73 8.60 5.79 6.37 C. I. Solvent Blue 35 3.90 7.54 5.25 5.56 C. I. Solvent Blue 59 2.09 5.42 4.54 4.02 C. I. Solvent Blue 68 3.08 5.66 4.56 4.43 C. I. Solvent Blue 79 1.41 4.36 3.91 3.23 C. I. Solvent Blue 90 3.98 6.54 4.69 5.07

Solvent red 27, Solvent yellow 56 and Solvent blue 14 selected according to Table 1 are the compounds represented by the following general formulas (1) to (3).

Solvent red 27

Solvent yellow 56

Solvent blue 14

Experiment 1: Dyeing experiment

3 g of polyolefin fabric (UHMWPE and HTPE) filaments were wound uniformly on a metal wire mesh tube to prepare specimens, and then washed with acetone to remove impurities remaining on the surface of the polyolefin filaments, followed by vacuum drying. To obtain optimum conditions for dyeing the polyolefin filaments, a three-color solvent dye, acetone, and distilled water were used to uniformly mix and then a saline solution was prepared at a bath ratio of 1:50. The polyolefin filaments prepared by uniformly winding the thus-prepared dye solution and metal wire mesh tube were placed in a high-pressure pot, and the dyeing temperature, dyeing time, dye concentration, and acetone content were measured using an IR stainer (Daelim Starlet DL-6000) And the polyolefin filament was stained. The high-temperature and high-pressure dyeing method was carried out to lower the dyeing initiation temperature to 40 ° C, 80 ° C to 130 ° C to 40 ° C at a heating rate of 2 ° C / min, a holding time of 20 to 240 minutes and a cooling rate of 2 ° C / min. The dyed polyolefin filaments were washed five times with acetone to remove unfixed dyes remaining on the surface of the polyolefin filament fabric, washed with distilled water at room temperature, and vacuum dried to prepare dye samples.

Experiment 2: Measurement of salt loading and evaluation of tensile properties

A sample prepared by vacuum drying to extract the dye in the dyed polyolefin filament was placed in a glass bottle containing 30 ml of 100% N, N-dimethylformamide (DMF) and extracted with stirring at 90 ° C for 3 hours. Standard solutions were prepared for each concentration using a three-color solvent dye and DMF, and the absorbance was measured at a maximum absorption wavelength from a saline solution of each concentration using a spectrophotometer (UV-Vis Spectrophotometer, UV-1800, Shimadzu) . The amount of dyed dye was calculated by using the absorbance of the salt solution extracted from the calibration curve and the dyed polyolefin filament. Also, the tensile strength and elongation characteristics of the three - color polyolefin filaments prepared according to the dyeing temperature and dyeing time were analyzed using a high temperature universal material testing machine (Instron 5980S) according to the KS K 0412 standard.

Experiment 3: Log P calculation and optical microscope analysis

To perform the logP calculations of the three primary color solvent dyes, the chemical structure of each dye was drawn using ChemDraw Ultra 12.0 software and the ALOGP and CLOGP values were determined from the chemical properties window. In addition, the ALOGPS values were calculated using the ALOGPS 2.1 program using the ChemDraw Ultra 12.0 software. On the other hand, after dyeing, the three-color high-strength polyethylene filament section was evaluated for color expression in the filament using an optical microscope (DM5500B).

Experiment 4: Polyethylene filament differential scanning method (DSC) analysis

Thermal analysis of the polyolefin filaments was carried out using a differential scanning calorimeter (DSC Q 20 (TA, USA)) at a heating rate of 5 ° C / min in a N ₂ stream.

Results and discussion

(1) 200 denier UHMWPE filament and textile dyeing and evaluation

① Dyeing and characterization of 200 denier UHMWP filaments using dispersant (Tween 20)

Since UHMWPE fibers have higher crystallinity and higher molecular weight than HTPE fibers, they are difficult to dye by the general seeping method and thus they are limited in application to medical and sports fields requiring various color expressions. In the present invention, a dyeing test was conducted using a dispersing agent, which is generally a method of dyeing ultra high molecular weight polyethylene woven fabric, and dyeability was evaluated.

FIG. 1 is a photograph showing the results of dyeing 200 denier UHMWPE filaments by using a dispersing agent. The dyeing temperature was 90-130 ° C., a general condition for dyeing 200 denier UHMWPE, the dyeing time was 1 hour, the dye concentration was 5% ≪ RTI ID = 0.0 > Tween 20 < / RTI > and a three-color solvent dye.

Referring to FIG. 1, it can be seen that the dyeability increases with increasing dyeing temperature regardless of the type of solvent dye, and the UHMWPE filaments are fused at a dyeing temperature of 140 ° C.

Also, when dyeing was carried out at a dyeing temperature of 120 ° C or lower, uniform and vivid hue was not expressed. Therefore, it is an experimental result that it is a problem to dye a high strength olefin fiber by using a dispersant and a new dyeing method which can improve dyeability is needed.

② Dyeing and characterization of 200denier UHMWP filament using acetone

FIG. 2 is a photograph showing the results of dyeing 200 denier UHMWPE filaments dyed at different dyeing temperatures under the condition of no dispersing agent according to the present invention, and FIG. 3 is a view showing the results of analysis of salt loading and tensile strength of each sample of FIG. 2 . FIG. 2 is a photograph of a sample prepared by keeping the dye concentration at 2.0% owf and the acetone content constant at 10% relative to the bath ratio, and then staining at a dyeing temperature of 80 to 130 ° C for 1 hour.

Referring to FIG. 2, it can be seen from the visual inspection that dyeing property increases with increasing dyeing temperature, darker color is expressed than sample prepared using dispersing agent, and dyeing at a temperature below 120 ° C Can be confirmed. However, the temperatures at which fusion occurred were similar. This result is considered to be due to the fact that the melting point of the ultrahigh molecular weight polyethylene is 133 ° C, as shown in the results of the DSC analysis, so that the dyeing temperature is maintained above the melting point.

Referring to FIG. 3, as in FIG. 2, the salt loading increased with increasing dyeing temperature, and the tensile strength decreased with increasing dyeing temperature and elongation increased, but the change in physical properties with temperature was insignificant see. In general polyolefin fibers, nylon and other fibers, the intensity decreases and the elongation increases as the dyeing temperature increases. However, the physical properties of the 200 denier UHMWPE filament used in the present invention hardly affect the dyeing temperature. The reason for this is considered to be that the ultrafast molecular weight polyethylene fabric has a high degree of crystallinity and a large molecular weight, so that the effect on physical properties is negligible. Therefore, the proper temperature for dyeing 200 denier UHMWPE filaments was 130 ℃.

In addition, the dyeing amount of ultrahigh molecular weight polyethylene fabric prepared by using dispersant (Tween 20) and acetone was compared with that of acetone. As a result, it was found that dyeing of fabric dyed with acetone at about twice the dyeing temperature Respectively. Therefore, it is considered that the acetone used for producing the saline solution has a considerable influence on the dyeability.

FIG. 4 is a photograph showing the results of dyeing 200 denier UHMWPE filaments stained for each dyeing time, and FIG. 5 is a graph showing the results of analysis of salt loading and tensile strength of each of the samples of FIG. The photographs of FIG. 4 are for UHMWPE filament samples stained at a dyeing temperature of 130 ° C, a dye concentration of 2.0% owf, and an organic solvent content of 10% relative to the bathing ratio, followed by dyeing time.

Referring to FIG. 4, it can be seen that the dyeability tends to increase as the dyeing time increases.

FIG. 5 shows changes in the amount of salt deposition and tensile strength with time of dyeing.

Referring to FIG. 5, as the dyeing time increased, the salt loading tended to be almost constant from 120 minutes or longer regardless of the type of dye, and the salt loading was also similar from 120 minutes or longer. Also, tensile strength decreased with increasing dyeing time and elongation tended to increase, but the difference was very small, within 1%.

On the other hand, when dyeing was performed using the three primary colors solvent dyes under the same conditions and the dyeing temperatures were compared according to the dyeing temperature, it was found that even if dye and acetone were used at the same concentration in the order of Solvent Yellow 56> Solvent Blue 14> Solvent Red 27, Respectively. As mentioned in Table 1, the dyes having a high hydrophobic value are expected to be in the order of Solvent Red 27> Solvent Blue 14> Solvent Yellow 56 in order of high affinity with high strength polyethylene filaments. However, according to the present invention, the salt loading of the three-color solvent dye is different from the log P value. According to the invention relating to the dyeing of polyester fibers using two kinds of disperse dyes, when supercritical fluid dyeing was carried out under the same conditions using Red 60 (anthraquinone) and Yellow 54 (quinoline) having different chemical structures, 60, dyeing equilibrium was reached within 240 minutes, Yellow 54 required dyeing time of 360 minutes or more, and Red 60 dye was 3-4 times higher in dyeing time at the same dyeing time. In a previous study (Park et al.), Diminopyridine azo red disperse dyes were synthesized to dye PET fabrics, and maximum absorption wavelength and molar extinction coefficient were analyzed. As a result, amino azobenzene dyes with red color It was confirmed that the color intensity was higher than that of the heterocyclic azo disperse dye. In addition, the difference in the molar extinction coefficient of the dye was mainly attributed to the polarity and planarity of the dye molecule. In order to dye pure polypropylene (PP) fibers and ultra high molecular weight polyethylene (UHMWPE) fibers in a conventional study (Kim et al.), It has been found that hydrogen bonds in the coupler aromatic rings of the monoazo dye matrix or anthraquinone dye matrix, , Methyl, ethyl, etc. Were synthesized and dyeing was carried out. As a result, the higher the hydrophobic group, the higher the dyeability and the amount of dyeing. Weaver, who analyzed azo dyes and anthraquinone dyes, found that the azo series are rich in color and are expressed, while the anthraquinone dyes have a low color value but a clear color and excellent dyeing properties.

However, depending on the dyeing temperature, the amount of ultrafine molecular weight polyethylene filament salt prepared according to the present invention varies depending on the dyeing temperature. However, as the dyeing time increases, the similar dyeing amount after about a certain time is about 0.13-0.15 g / g fiber, . In order to investigate the effect of hydrophobicity on the dyeability, dyeing temperature and dyeing time were investigated using Solvent 97 and Solvent 14, which had the same chemical structure but different hydrophobic values. In order to examine the dyeability of the ultra high molecular weight polyethylene fabric, owf, acetone content of 10% and water were added to maintain the bath ratio at 1:50, dyeing was carried out at 130 ℃ for 2 hours, and the salt loading was compared.

Table 2 shows the results of Log P, molecular weight and salt loading of Solvent 97 and Solvent 14, and sample photographs of dyeing temperature are shown in FIG.

dyes rescue Molecular Weight
(MW) LOGP CLOGP ALOGPS Average Salt loading
(g / gfiber) Solvent 14 Anthraquinone 380.85 4.73 8.60 5.79 6.37 0.14 Solvent 97 530.70 9.94 13.44 7.17 10.18 0.03

FIG. 6 is a photograph showing the results of dyeing Solvent 97 and Solvent 14 by the dyeing temperature.

Referring to Table 2 and FIG. 6, it was found that when dyeing was performed using Solvent Blue 97 and 14 having the same chemical structure and different molecular weights and LogP values, the log P value at the same temperature was large, . Also, as the hydrophobicity increases, the particle size of the dye tends to increase because the molecular weight increases. According to the results of Kim et al., An alkyl group was added to an anthraquinone matrix to produce a dye, and dyeability was evaluated. When the number of alkyl groups was 8 or less, the dyeability was increased. As the alkyl group increases, the hydrophobicity increases and the molecular weight increases. That is, when the particle size of the dye is too large, a problem arises in dyeability. Therefore, it is considered that the dyeing amount of the ultrahigh molecular weight polyolefin woven fabric greatly affects the dyeing property by the hydrophobic value and the particle size of the dye.

FIG. 7 shows photographs of dyeing results of 200 denier UHMWPE filaments dyed by dye concentration, and FIG. 8 is a diagram showing the results of analysis of the salt amount of each of the samples of FIG. FIGS. 7 and 8 are for ultra-high molecular weight polyethylene filament samples prepared at dyeing temperature of 130 ° C., dyeing time of 120 minutes, and dye concentration after being kept constant at 10% with respect to the acetone content.

Referring to FIGS. 7 and 8, as the dye concentration was increased, the salt loading was increased, but the salt loading was similar at 2.0% owf or more. In general, when UHMWPE is dyed, it is known that dyeing is not performed at 1.0% or less. However, in the present invention, color is expressed even at a low concentration of 0.3% owf.

 On the other hand, in this study, it is possible to control the dye particle size in the salt solution by using an organic solvent. However, when the organic solvent is used, the boiling point is lower than that of water. Therefore, the internal pressure in the dye port increases during the dyeing process. Therefore, in order to investigate the effect of the organic solvent content on the UHMWPE filament, the organic solvent content was varied.

FIG. 9 is a photograph showing the result of dyeing 200 denier UHMWPE filament according to acetone content, and FIG. 10 is a diagram showing the result of analysis of the salt amount of each sample of FIG. FIGS. 9 and 10 show dyeing samples prepared by keeping the dyeing temperature at 130.degree. C., a dye concentration of 2.0% owf, and a dyeing time of 2 hours, and adjusting the organic solvent to 5% to 40% relative to the bathing ratio.

Referring to FIG. 9 and FIG. 10, dyeing properties were increased and decreased with increasing organic solvent regardless of the type of the three-color solvent dye. Solvent Yellow 56 showed the best dyeability when the organic solvent content was 5%, Solvent Red 24 was 30%, Solvent Blue 14 was 20%, and the dyeing amount was almost constant regardless of the type of solvent dye . However, depending on the type of solvent dye, the amount of adsorption varies depending on acetone content. These results show that the lower the molecular weight of the dye, the lower the acetone content, and the higher the molecular weight, the greater the acetone content. In addition, above a certain concentration of acetone content, it is considered that the dye is not stained because it is more stable in the acetone than the affinity of the dye with the ultrahigh molecular weight polyethylene fabric. That is, there is an appropriate particle size depending on the dye type. Therefore, the particle size of the three-color dye according to the acetone content is analyzed and shown in Table 3 below.

Particle size (D50 (占 퐉)) Solvent Yellow 56 Solvent Red 24 Solvent Blue 14 Acetone 5% 0.187 1.258 0.562 Acetone 10% Not measured 0.854 0.342 Acetone 15% Not measured 0.558 0.204 Acetone 20% Not measured 0.295 0.176 Acetone 30% Not measured 0.196 Not measured Acetone 40% Not measured Not measured Not measured

As shown in Table 3, the size of the dye was decreased as the acetone content was increased. Solvent Yellow 56 had an acetone content of 5% and a particle size of about 187 nm And the particle size was not measured as the acetone content was increased. Solvent Red 24 decreased in particle size from 1.258 ㎛ to 196 nm with increasing acetone content and particle size could not be measured with 40% acetone. On the other hand, in the case of Solvent Blue 14, the particle size was decreased from 562 nm to 176 nm as the acetone content increased, and the particle size was not measurable from the acetone content exceeding 30%. The acetone content varies depending on the type of dye, as mentioned above, because the molecular weight of the dye is different. That is, it can be seen that the smaller the molecular weight, the lower the acetone content used. In addition, when acetone above a certain amount was used, the size of the dye could not be measured due to the ionization of the dye. Solvent Blue 14 and Solvent Blue 97, which have different hydrophobic values and molecular weights, were analyzed for dyeability according to dyeing temperature. Solvent Blue 97 had a lower hydrophobicity than Solvent Blue 14. This is because the acetone content, which controls the particle size of the dye, is not adequate. Thus, a mixed bath was prepared by controlling the content of Solvent Blue 97 and acetone, and dyeing temperature, 130 ° C., dyeing time of 2 hours, dye concentration of 2% owf and bath ratio of 1:50 were maintained, and ultra high molecular weight polyethylene filament dyeing was carried out .

FIG. 11 is a photograph of a sample stained using Solvent Blue 97 according to an acetone content, and FIG. 12 is a view showing a tensile strength and strength analysis result of each sample of FIG.

Referring to FIG. 11, it can be seen that the dyeability increases with increasing acetone content. The results of dyeing temperature, dyeing time, dye concentration, and acetone content showed that when dyeing polyolefin fabrics with solvent dyes, the factors affecting dyeability were not the chemical structure or molecular weight but the hydrophobicity and particle size It is judged to have a lot of influence.

12, even if the organic solvent content is increased, the tensile strength of the filament is slightly decreased and the elongation is increased, but the properties of the filament are not greatly changed.

(2) 200 denier UHMWPE fabric dyeing and fastness, colorimetric analysis

Based on the result of 200 denier UHMWPE filament dyeing, UHMWPE fabric dyeing experiment was carried out as shown in Table 4. As a result, wash fastness, friction fastness, seawater fastness, light fastness and color fastness of 200 denier UHMWPE fabrics stained as shown in FIG. 13 are shown in Table 5 below.

turn dyes Concentration (%) Temperature (℃) Time (min) Bath Organic solvent (%) One Red 24 2 130 120 1:50 30 2 Yellow 56 5 3 Blue 14 20

turn Test Items Color Blue Yellow Red One Color yield 150% or more 116% or more 150% or more 2 Wash fastness 4-5 3 Friction fastness 4-5 4 Light fastness 4 or more 5 Seawater fastness 4-5

FIG. 13 is a photograph showing the results of staining of UHMWPE filaments stained with a three-color solvent dye.

Referring to Tables 4 and 5 and FIG. 13, the color of the dyed UHMWPE fabrics was higher than that of Red 150%, Yellow 116%, Blue 150%, and was excellent in washing, friction, seawater fastness 4-5, It can be confirmed that the fastness is excellent at the grade 4 or higher.

(3) 200denier  High Strength Polyethylene ( HTPE ) Evaluation of dyeability and physical properties of filaments and fabrics

① Dyeing property and property evaluation of 200denier HTPE filament according to dyeing temperature

FIG. 14 is a photograph showing the results of dyeing 200 denier HTPE filaments according to dyeing temperature, and FIG. 15 is a diagram showing the results of analysis of salt loading and tensile strength of each sample of FIG.

FIG. 14 shows the result of dyeing the 200 denier HTPE filaments, keeping the dye concentration at 1% owf, the organic solvent and the dispersant at 10%, and the bath ratio at 1:50, staining the dyeing temperature at 70 to 130 ° C for 60 minutes, And the obtained samples.

Referring to FIG. 14, as the dyeing temperature was increased, the dyeability tended to increase irrespective of the type of dye. At 130 ° C, fusion of filaments occurred. This result is due to dyeing at a dyeing temperature of 131 ° C, which is the melting point of 200 denier HTPE filament, by DSC analysis.

As shown in FIG. 15, as the dyeing temperature was increased, the amount of dye of the three-color dye tended to increase, and the change in the amount of dyeing was less than 100 ° C. Also, the tensile strength decreased with increasing dyeing temperature, and the strength at 90 ~ 120 ℃ was about 90 ~ 80% compared to filament before dyeing. The elongation tended to increase with increasing dyeing temperature and the maximum elongation at 120 ℃ was about 44%. Therefore, the temperature suitable for 200denir HTPE filament dyeing is considered to be 100 ° C, which has a small effect on tensile strength and a high salt loading.

② Dyeing property and property evaluation of 200denier HTPE filament according to dyeing time

 In order to confirm dyeability of 200 denier HTPE filament according to dyeing time, a dye was prepared so as to have a dye concentration of 1% owf, an organic solvent and a dispersant content of 10% and a bath ratio of 1:50, and the dyeing time was adjusted to 20 to 240 min at a dyeing temperature of 100 ° C A dye sample was prepared.

FIG. 16 is a photograph showing the results of dyeing 200 denier HTPE filaments per dyeing time, and FIG. 17 is a diagram showing the results of analysis of salt loading and tensile strength of each sample of FIG.

Referring to FIG. 16 and FIG. 17, the dyeability of the dye sample is almost similar regardless of the dyeing time. Salinity and tensile strength were analyzed to confirm the more accurate dyeing and physical properties. Figure 18 shows the results of the analysis of the amount of salt deposition and tensile strength according to dyeing time. As the dyeing time increased, the amount of dyeing increased slightly, but the amount of dyeing was almost similar from 60 minutes or longer. The reason for the difference in the amount of dye depending on the type of dyes seems to be influenced by dye structure, dyeing temperature and size. Therefore, it is considered that 60 minutes, which maintains the intensity of 90% level while having a high salt amount, is a suitable dyeing time.

③ Evaluation of dyeability of 200denier HTPE filament according to dye concentration

After maintaining the dyeing temperature at 100 ° C., dyeing time 60 min, the organic solvent and dispersant content 10%, and the bath ratio 1:50, the dye concentration was adjusted to 0.3~7.0% owf and washed with acetone to prepare samples.

FIG. 18 is a photograph showing the result of dyeing 200 denier HTPE filament according to dye concentration, and FIG. 19 is a diagram showing the result of analysis of the salt amount of each sample of FIG. 18.

18 and 19, the amount of 200 denier HTPE filaments dyed according to the dye concentration was measured. As a result, the amounts of dyeing were almost similar from the dye concentration of 1.0% owf or more regardless of the type of the three-color solvent dye. Therefore, the most efficient dye concentration for 200 denier HTPE filament dyeing is estimated to be 1% owf.

④ Dyeing property and property evaluation of 200denier HTPE filament according to organic solvent content

 The ultrafine molecular weight polyethylene (UHMWPE) filament and fabric dyeing showed that the optimum organic solvent content was present depending on the type of dye. Therefore, it is important to determine the optimal organic solvent content of the three-color solvent dye when the dyeing temperature is 100 ° C. To determine the effect of the organic solvent content on the dyeability of 200 denier HTPE filaments, the dyeing temperature was adjusted to 100 ° C., dyeing time 1 hour, dye concentration 1% owf and bathing ratio 1:50, and the content of acetone was changed from 5 to 50% And the dyeing characteristics were evaluated.

FIG. 20 is a photograph showing the results of dyeing 200 denier HTPE filaments according to acetone content, and FIG. 21 is a diagram showing the results of analysis of salt loading and tensile strength of each sample of FIG. 20.

20 and 21, as a result of analyzing a sample photograph of the three-color-red dye by changing the organic solvent content, the dyeability was increased with an increase in the organic solvent content, but the dyeability was lowered below a certain content.

As shown in FIG. 20, when the amount of acetone was measured, the results were similar to those of visual inspection. Solvent Yellow 56 had an organic solvent content of 10%, Solvent Red 24 was 20% and Solvent Blue 14 was 15% It can be confirmed that a high amount of the dye is present. Also, it can be seen that the organic solvent content did not significantly affect the tensile strength change. However, the organic solvent content of the 200 denier UHMWPE mentioned above was different from 200 denier HTPE filament dyeing depending on the type of dye, but the amount of salt was almost similar. However, in the case of 200 denier HTPE filaments, the amount of dye was different depending on the type of dye. These results are due to the fact that the particle size was controlled according to the type of dye but the dyeing temperature was relatively low which could improve the dyeability. That is, it can be seen that there is an acetone content that can exhibit optimal dyeability depending on the dyeing temperature.

⑤ Dyeing and fastness evaluation of 200denier HTPE fabric and HTPE / PET blend fabric

 From 200 denier HTPE filament staining results, dyeing experiment of 200 denier HTPE fabric and HTPE / PET blend fabric was carried out and the fastness was evaluated.

FIG. 22 is a photograph showing a 200 denier HTPE fabric dyed sample and HTPE / PET mixed fabric sample photographs, and FIG. 23 is a photograph showing a surface and a cross section of a 200 denier HTPE fabric dyed sample.

22 and 23, the surface and cross-sectional photographs of the fabric dyed using the organic solvent and the three-color solvent dye were taken to show uniform dyes not only on the surface but also on the surface of the filament.

turn Test Items Color Blue Yellow Red One Color yield PET: 112%,
Nylon: 105% PET: 89%,
Nylon: 103% PET: 116%,
Nylon: 107% 2 Wash fastness 4-5 3 Friction fastness 4-5 4 Light fastness Level 4 or higher 5 Seawater fastness 4-5

turn Test Items Color Blue Yellow Red One Color yield PET: 116%,
Nylon: 109% PET: 90%,
Nylon: 104% PET: 120%,
Nylon: 112% 2 Wash fastness Level 3 or higher 3 Friction fastness 4-5 4 Light fastness Level 3 or higher 5 Seawater fastness 4-5

As shown in Table 6 and Table 7, both of the 200 denier HTPE fabric and the HTPE / PET blend fabric exhibited a fastness of 4 or higher in light fastness, and a fastness of 4 to 5 in washing, friction and seawater fastness.

(4) 135denier  High Strength Polyethylene ( HTPE ) Evaluation of dyeability and physical properties of filaments and fabrics

 200denier UHMWPE and HTPE filament and fabric, we evaluated the effect of dyeing temperature, dyeing time and dye concentration on dyeability and mechanical properties of 100denier grade HTPE filaments and fabrics in order to derive optimal dyeing conditions. The dyeing and tensile strength of the dyed filaments was carried out in the same manner as for the analysis of 200 denier HTPE filaments.

① Dyeing property and property evaluation of 100denier HTPE filament according to dyeing temperature

To investigate the effect of 100 denier grade filament on dyeing temperature, three-color filament dye samples obtained by changing the dyeing temperature after keeping dye concentration 1% owf, dyeing time 60 min, bathing ratio 1:50 and organic solvent content 10% ≪ / RTI >

FIG. 24 is a view showing photographs of 100 denier grade filament three-color dyed samples for each dyeing temperature, and FIG. 25 is a view showing the results of analysis of salt loading and tensile strength of each sample of FIG.

Referring to FIG. 24 and FIG. 25, dyeing properties tend to be almost similar from 70 ° C or more regardless of the type of dye. Figure 27 shows the change in salt loading and tensile strength according to dyeing temperature. As the dyeing temperature increased, the amount of dyeing increased gradually, and the elongation tended to increase with increasing dyeing temperature. In the case of the high-strength polyethylene filament produced by the present invention, the dyeability is important but the strength retention is also important. As a result of the analysis of dyeability and tensile strength, it is judged that the appropriate dyeing temperature is 80 ℃.

② Dyeing property and physical property evaluation of 100denier HTPE filament according to dyeing time

Dyeing temperature was 80 ℃, dye concentration was 1% owf, bath ratio was 1:50 and organic solvent content was kept constant at 10%. Dyeing time was evaluated according to dyeing time.

FIG. 26 is a view showing photographs of 100 denier grade filament three-color-stained samples by dying time, FIG. 27 is a view showing a result of analysis of the salt amount of each sample of FIG. 26, FIG. 28 is a graph showing tensile strength Fig.

Referring to FIGS. 26, 27 and 28, although the amount of salt is different depending on the kind of dye, the amount of dyeing seems to be almost similar from the dyeing time of 60 minutes or more. Figure 30 shows the tensile strength change with time of dyeing. Therefore, the dyeing time suitable for 100 denier grade HTPE filament dyeing is 60 min.

③ Evaluation of dyeability of 100denier grade HTPE filament according to dye concentration

 Dyeing temperature was 80 ℃, dyeing time was 60min, bathing ratio was 1:50 and organic solvent content was kept constant at 10%. Dyeability was evaluated according to dye concentration.

FIG. 29 shows photographs of 100 denier grade filament three-color dyed samples by dye concentration, and FIG. 30 is a diagram showing the results of analysis of the salt amount of samples of FIG. 29.

Referring to FIGS. 29 and 30, it was found that the dyeing amount of the 100 denier HTPE filament according to the dye concentration was similar to that of the 200 denier HTPE filament, and the dyeing amount was similar from the dye concentration of 1.0% appear. Therefore, it is considered that the effective dye concentration for 100 denier grade HTPE filament dyeing is 1% owf.

④ 100 denier grade HTPE textile dyeing

 100 denier grade HTPE filament dyeing results are shown in Table 8, dyeing temperature 80 ° C., dyeing time 60 min, dye concentration 1.0% owf, bathing ratio 1:50, .

turn textile dyes Dye concentration (% owf) Organic solvent
(%) Dyeing time
(min) Dyeing temperature
(° C) One 100denier grade HTPE Red 24 One 20 60min 80 2 Yellow 56 5 3 Blue 14 15

31 is a photograph showing a 100-denier grade fabric three-color-stained samples.

Referring to FIG. 31, it can be seen that uniform and dense tricolor hues are well expressed in the dyed 100 denier grade HTPE fabric samples.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.

Claims (5)

Diluting a salt solution containing a solvent dye and acetone with water to prepare a dyeing solution;
Adding a fabric composed of polyolefin fibers to the dyeing solution to dye;
Cleaning the dyed fabric; And
≪ / RTI >
Method of dyeing polyolefinic fabrics.
The method according to claim 1,
Characterized in that the dyeing step is carried out at a temperature of less than < RTI ID = 0.0 > 130 C < / RTI &
Method of dyeing polyolefinic fabrics.
The method according to claim 1,
The content of acetone in the saline solution was
By weight based on the total weight of the saline solution.
Method of dyeing polyolefinic fabrics.
The method according to claim 1,
When the solvent dye is Solvent Yellow 56, the content of acetone in the saline solution is 5 wt% based on the total weight of the saline solution,
When the solvent dye is Solvent Red 24, the content of acetone in the saline solution is 40 wt% based on the total weight of the saline solution,
Wherein when the solvent dye is Solvent Blue 14, the content of acetone in the salt solution is 20% by weight based on the total weight of the salt solution.
Method of dyeing polyolefinic fabrics.
The method according to claim 1,
Wherein the cleaning step is to remove solvent dyestuff remaining unchained in the dyed polyolefinic fabric using acetone,
Characterized in that a separate reduction washing process is not performed.
Method of dyeing polyolefinic fabrics.

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